WO2011156921A2 - Catalyst ligands, catalytic ligand complexes and polymerization processes using same - Google Patents

Catalyst ligands, catalytic ligand complexes and polymerization processes using same Download PDF

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Publication number
WO2011156921A2
WO2011156921A2 PCT/CA2011/050359 CA2011050359W WO2011156921A2 WO 2011156921 A2 WO2011156921 A2 WO 2011156921A2 CA 2011050359 W CA2011050359 W CA 2011050359W WO 2011156921 A2 WO2011156921 A2 WO 2011156921A2
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Prior art keywords
heteroatom
hydrocarbyl
substituted hydrocarbyl
attached
substituted
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PCT/CA2011/050359
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French (fr)
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WO2011156921A3 (en
Inventor
Gino Georges Lavoie
Sarim Dastgir
Barbara Caroline Skrela
Timothy Gordon Larocque
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Gino Georges Lavoie
Sarim Dastgir
Barbara Caroline Skrela
Timothy Gordon Larocque
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Publication of WO2011156921A2 publication Critical patent/WO2011156921A2/en
Publication of WO2011156921A3 publication Critical patent/WO2011156921A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to organic compounds as ligands, catalytic metal complexes formed with such ligands and the use of such catalysts in polymerization reactions and other bond forming reactions.
  • ligands organic compounds as ligands
  • catalytic metal complexes formed with such ligands and the use of such catalysts in polymerization reactions and other bond forming reactions.
  • Olefin polymers have a wide variety of industrial uses and are therefore economically important.
  • the polymerization reactions used to form such polymers utilize catalysts, primarily comprising a metal and organic ligand complex.
  • Some of the catalysts developed for polymerization reactions are cationic. These cationic catalysts generally comprise neutral alpha-diimine ancillary ligands coordinated, or complexed with transition metals, in particular, late transition metals (i.e. a metal from Group 8-10). Examples of such cationic catalysts are provided Chem. Rev. 2000, 100(4), 1 169. Chem. Rev. 2003, 103(1), 283, Angew. Chem. Int. Ed.
  • catalysts comprise an anionic ligand coordinated to late transition metals.
  • neutral catalysts have been found to be more tolerant of functional groups on monomers, they have also been found to be significantly less active than the cationic catalysts discussed above. Examples of such neutral catalysts are provided in Science 2000, 287(5452), 460, WO 01/92342, WO 01/68724.
  • nitrogen As a donor atom in ligands, its heavier congener phosphorus has also been used.
  • the use of a phosphine donor has led to enhanced thermal stability over the nitrogen analogue. This is thought to be due to the stronger metal-phosphorus bond strength, resulting in an increased binding constant.
  • cationic catalysts result in a desired degree of catalytic activity but suffer from being less tolerant to functional groups that are present on monomers (i.e. more prone to poisoning).
  • Neutral catalysts are more tolerant of monomer functional groups but are less active.
  • zwitterionic catalysts have also be proposed. An example of such zwitterionic catalyst is provided in US Publication number US 2002/0028741 and WO 2002/049758.
  • the present invention provides compound as ligands and precursors for use in a coordination complex.
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 21 is selected from hydrocarbyl, and substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydro
  • the substituent may be further substituted by up to 3 Ci -6 alkyl groups; R 20 and R 22 may be taken together with C 2 and E 4 to form a ring; G 2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G 2 and E 2 may be connected by either a single bond or a double bond; G 2 and E 5 may be connected by either a single bond or a double bond; E 1 is selected from nitrogen, oxygen and sulfur; E 2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E 3 is selected from carbon, nitrogen, oxygen and sulfur; E 4 is selected from carbon and phosphorus; E 5 is selected from carbon and boron; E 2 and E 3 may be connected by either a single bond or a double bond; X " is chloride, bromide, iodide, BF 4 " , PF 6 "
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring;
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl
  • G 2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G 2 and E 2 may be connected by either a single bond or a double bond; G 2 and E 5 may be connected by either a single bond or a double bond; E 1 is selected from nitrogen, oxygen and sulfur E 2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E 3 is selected from carbon, nitrogen, oxygen and sulfur; E 5 is selected from carbon and boron; E 6 is selected from oxygen, sulfur and nitrogen; E 2 and E 3 may be connected by either a single bond or a double bond; M + is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i is 0, E 2 and E 5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • G 2 and E 2 may be connected by either a single bond or a double bond
  • G 2 and E 5 may be connected by either a single bond or a double bond
  • E 1 is selected from nitrogen, oxygen and sulfur
  • E 2 is selected from carbon, nitrogen, oxygen, sulfur and boron
  • E 3 is selected from carbon, nitrogen, oxygen and sulfur
  • E 4 is selected from carbon, phosphorus and sulfur
  • E 5 is selected from carbon and boron
  • E 2 and E 3 may be connected by either a single bond or a double bond
  • X " is chloride, bromide, iodide, BF 4 " , PF 6 " , tosylate, mesylate, B(C 6 F 5 ) 4 " , 3,5-(C 6 H3)-(CF 3 )2 " or other common anions
  • i is 0 or 1 when i is 0, E 2 and E 5 may either not be connected by any bond
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • G 2 and E 2 may be connected by either a single bond or a double bond
  • G 2 and E 5 may be connected by either a single bond or a double bond
  • E 1 is selected from nitrogen, oxygen and sulfur
  • E 2 is selected from carbon, nitrogen, oxygen, sulfur and boron
  • E 3 is selected from carbon, nitrogen, oxygen and sulfur
  • E 4 is selected from carbon and phosphorus
  • E 5 is selected from carbon and boron
  • E 2 and E 3 may be connected by either a single bond or a double bond
  • X " is chloride, bromide, iodide, BF 4 " , PF 6 " , tosylate, mesylate, B(C 6 F 5 ) 4 ⁇ , 3,5-(C 6 H 3 )-(CF 3 ) 2 " or other common anions
  • i is 0 or 1 ; when i is 0, E 2 and E 5 may either not be connected by
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring;
  • R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydro
  • a catalytic system comprising at least one compound according to any one of formulas I to IX as defined above and a transition metal compound or complex.
  • a further aspect of the invention is the utility of the catalytic system to catalyze bond forming reactions including polymerization, copolymerization, cross-coupling reactions, hydroformylation, hydrogenation, hydrosilylation and hydroboration.
  • Figure 1 shows the solid state molecular structure of amidinium salts 3a and 3b determined by single crystal X-ray diffraction studies. Thermal ellipsoids are drawn at 40% probability. Hydrogen atoms and solvent molecules (CH 2 CI 2 ) are omitted for clarity.
  • Figure 2 shows the solid state molecular structure of 4a as determined by single crystal X-ray diffraction studies. Thermal ellipsoids are drawn at 40% probability. Hydrogen atoms and solvent molecule (CHCI 3 ) have been removed for clarity.
  • Figure 3 shows the solid state molecular structure of 5a as determined by single crystal X-ray diffraction studies. Thermal ellipsoids are drawn at 40% probability. Hydrogen atoms and solvent molecule (CH 2 CI 2 ) have been removed for clarity. DETAILED DESCRIPTION OF THE INVENTION [0022]
  • polymerization refers to a process wherein at least two olefin molecules are combined into a single molecule (“dimerized”), or an oligomer or polymer is formed.
  • the average degree of polymerization is 5 or more, more preferably about 10 more, and especially preferably about 25 or more.
  • polymer refers to a species comprised of monomer units and having a degree of polymerization (DP) of 10 or higher.
  • DP degree of polymerization
  • the terms "monomer” or “olefin monomer” refer to the olefin or other monomer compound before it has been polymerized.
  • the term “monomer units” refers to the monomer moieties that are combined together to form a polymer, after they have been polymerized.
  • Ngand refers to an ionic or neutral molecule that binds to a central metal atom to form a coordination complex.
  • C, H, N, O, S, P, and Si stand for carbon, hydrogen, nitrogen, oxygen, sulfur, phosphorus and silicon, respectively.
  • hydrocarbyl means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms, and may be saturated or unsaturated.
  • monovalent hydrocarbyls include the following: C 1 -C 20 alkyl; C 3 -C 8 cycloalkyl or C 6 -C 14 aryl.
  • Cyclic hydrocarbyls may include mono or multiclyclic ring systems.
  • divalent (bridging hydrocarbyls) examples include: --CH 2 -, ⁇ CH 2 CH 2 -, -C 6 H 4 -, and -CH 2 CH 2 CH 2 -.
  • substituted hydrocarbyl refers to a hydrocarbyl substituted with one or more groups selected from C C 20 alkyl, C 3 -C 8 cycloalkyl or C 6 -C 14 aryl; In an embodiment the substituted hydrocarbyl includes one to four substituents as described above.
  • aryl refers to an aromatic group having 6 to 14 carbon atoms.
  • aryl groups include phenyl, naphthyl, and anthracenyl groups.
  • Aryl may also refer to a cyclic aromatic group having 5 to 14 members if one or more of the members are heteroatoms selected from O, N and S.
  • a "heteroatom” refers to an atom other than carbon or hydrogen. Examples of heteroatoms include oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, silicon, chlorine, bromine, and fluorine.
  • a "heteroatom substituted hydrocarbyl” refers to i) a monovalent or divalent hydrocarbyl substituted with one or more heteroatoms.
  • Examples of monovalent heteroatom substituted hydrocarbyls include: trifluoromethyl, 2,6- dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4- methoxycarbonyl-2,6-dimethylphenyl.
  • hydrocarbyls include 4-methoxy-1 ,2-phenylene, 1-methoxymethyl-1 ,2-ethanediyl, 1 ,2- bis(benzyloxymethyl)-1 ,2-ethanediyl, and 1-(4-methoxyphenyl)-1 ,2-ethanediyl; ii) a C C 20 alkyl wherein from 1 to 6 carbon atoms are replaced with heteroatoms selected from oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, silicon and/or wherein 1-12 of the hydrogens atoms are replaced with chlorine, bromine, and/or fluorine and wherein the number of carbon and/or hydrogen atoms replaced will be suitably selected based on the number of carbon and hydrogen atoms in the alkyl chain; iii) a C 3 -C 8 cycloalkyl wherein from 1 to 4 carbon atoms are replaced with heteroatoms selected from oxygen, nitrogen, sulfur, and/or wherein 1-8 of the hydrogens
  • monovalent and divalent heteroatom substituted hydrocarbyls and hydroaryls include: methoxymethyl, diphenylphosphinemethyl, 2-furyl, 3-furyl, 2-pyridinyl, 3- pyridinyl, 4-pyridinyl, 2-thiophenyl, 3-thiophenyl, 2-oxazolyl, 4-imidazolyl, 4-imidazolidinyl, 2- imidazolidinyl, 2,3-dihydrobenzimidazol-2-yl, 2-piperidinyl, phenoxymethyl, tetrahydropyran- 2,6-diyl, 1 '-ethoxyethane-2,2'-diyl, and derivatives thereof.
  • substituted heteroatom substituted hydrocarbyl refers to a heteroatom substituted hydrocarbyl that is further substituted with one or more groups selected from C C 2 o alkyl, C 3 -C 8 cycloalkyl or C 6 -C 14 aryl; In an embodiment the substituted heteroatom substituted hydrocarbyl includes one to four substituents as described above.
  • heteroatom attached hydrocarbyl refers to a hydrocarbyl group that is attached or bound to a heteroatom that is in turn attached or bound to the remainder of the molecule.
  • heteroatom attached hydrocarbyl examples include: methoxy (OCH 3 ), ethoxy (OCH 2 CH 3 ), phenoxy (0(C 6 H 5 ), dimethylamine (N(CH 3 ) 2 ), diphenylphosphine (P(C 6 H 5 ) 2 ).
  • heteroatom attached substituted hydrocarbyl refers to a substituted hydrocarbyl or to a heteroatom substituted hydrocarbyl, or to a substituted heteroatom substituted hydrocarbyl respectively, as defined above, that is attached or bound to a heteroatom that is in turn attached or bound to the remainder of the molecule.
  • silicon-attached hydrocarbyl and "tin-attached hydrocarbyl” refer to a hydrocarbyl group that is attached or bound to a silicon or tin atom respectively, and the silicon or tin atom is in turn attached or bound to the remainder of the molecule.
  • the present invention is based upon the development of a new ligand scaffold that has a fragment and that, by nature of its chemical composition, can adopt at least one mesomeric (resonance) form that is zwitterionic.
  • zwitterions are molecules that have both a formal positive and negative charge on different atoms within the molecules, but with a net or overall charge of zero.
  • zwitterions are overall neutral.
  • the invention takes advantage of the mesomeric characteristic, resulting in one of the possible donor atoms involved in coordinating to a metal centre, namely N 1 , being overall partially negatively charged by nature of the possible mesomeric structures, some of which would lead to a formally negative charge on one of the donor atoms and some of which would lead to a neutral (zero) charge on that same donor atom.
  • N 1 one of the potential donor atoms on the ligand, namely N 1 , would only bear a partial negative charge, thus conferring some unique properties to the ligand of the invention.
  • the partially negatively charged donor atom on the ligands of the invention results in metal catalyst active centres that are relatively electron rich and less electrophilic compared to a system where the partially negatively charged donor atom is replaced by a neutral donor atom.
  • the catalysts of the invention will therefore undergo oxidative addition, and migratory insertion into carbon monoxide and olefins more readily. This results, in many cases, in catalysts that are more active and more productive.
  • the decrease in the electrophilicity of the metal centre also mitigates and even eliminates the potential of the catalyst being poisoned by a Lewis base (e.g. a monomer having a functional group that functions as a Lewis base). As discussed above, such poisoning was found to be a severe limitation of other known systems.
  • the invention makes it possible to conduct reactions between the metal complexes coordinated by the ligands disclosed herein and substrates containing functional groups (e.g. functionalized olefins, such as acrylates).
  • functional groups e.g. functionalized olefins, such as acrylates.
  • the metal complexes coordinated by the ligands of the invention may be used to polymerize functional group containing vinyl monomers.
  • the metal complexes coordinated by the ligands of the invention may be used to polymerize olefins in the presence of less expensive cocatalysts.
  • the partially negatively charged donor of the ligand of the invention allows for a balance between the activity of the catalyst and the tolerance of functional groups.
  • the olefin polymerization catalysts of the present invention comprise transition metal complexes of bidentate ligands with said bidentate ligand being comprised of a fragment that is zwitterionic where one of the possible donor atoms, N 1 , bears a partially negative charge due to the possible mesomeric structures.
  • the invention provides a compound of formula (I):
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 21 is selected from hydrocarbyl, and substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydro
  • R 20 and R 22 may be taken together with C 2 and E 4 to form a ring;
  • G 2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • G 2 and E 2 may be connected by either a single bond or a double bond;
  • G 2 and E 5 may be connected by either a single bond or a double bond;
  • E 1 is selected from nitrogen, oxygen and sulfur;
  • E 2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
  • E 3 is selected from carbon, nitrogen, oxygen and sulfur;
  • E 4 is selected from carbon and phosphorus;
  • E 5 is selected from carbon and boron;
  • E 2 and E 3 may be connected by either a single bond or a double bond;
  • X " is chloride, bromide, iodide, BF 4 " , PF 6 " , tos
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring;
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydro
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring;
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydro
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • G 2 and E 2 may be connected by either a single bond or a double bond
  • G 2 and E 5 may be connected by either a single bond or a double bond
  • E 1 is selected from nitrogen, oxygen and sulfur
  • E 2 is selected from carbon, nitrogen, oxygen, sulfur and boron
  • E 3 is selected from carbon, nitrogen, oxygen and sulfur
  • E 4 is selected from carbon, phosphorus and sulfur
  • E 5 is selected from carbon and boron
  • E 2 and E 3 may be connected by either a single bond or a double bond
  • X " is chloride, bromide, iodide, BF 4 " , PF 6 " , tosylate, mesylate, B(C 6 F 5 ) 4 ⁇ , 3,5-(C 6 H3)-(CF 3 )2 " or other common anions
  • i is 0 or 1 ; when i is 0, E 2 and E 5 may either not be connected by
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • G 2 and E 2 may be connected by either a single bond or a double bond
  • G 2 and E 5 may be connected by either a single bond or a double bond
  • E 1 is selected from nitrogen, oxygen and sulfur
  • E 2 is selected from carbon, nitrogen, oxygen, sulfur and boron
  • E 3 is selected from carbon, nitrogen, oxygen and sulfur
  • E 4 is selected from carbon and phosphorus
  • E 5 is selected from carbon and boron
  • E 2 and E 3 may be connected by either a single bond or a double bond
  • X " is chloride, bromide, iodide, BF 4 " , PF 6 " , tosylate, mesylate, B(C 6 F 5 ) 4 ⁇ , 3,5-(C 6 H3)-(CF 3 )2 " or other common anions
  • i is 0 or 1 ; when i is 0, E 2 and E 5 may either not be connected by any bond
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring;
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydro
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with C 4 , C 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 21 is selected from hydrocarbyl, and substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarby
  • the substituent may be further substituted by up to 3 C1-6 alkyl groups; R 20 and R 22 may be taken together with C 2 and E 4 to form a ring; E 4 is selected from carbon and phosphorus; X " is chloride, bromide, iodide, BF 4 " , PF 6 " , tosylate, mesylate, or other common anions; i is 0, in which case C 4 and C 5 may either not be connected by any bond, or alternatively, may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N 1 and E 4 are connected to each other by either single, double or triple bonds; g is 0, 1 , 2 and is chosen to obey the valency of C 2 ; k is O, 1 or 2; m is 1 or 2 and is chosen to obey the valency of the E 4 ; and with the proviso that the compound is not 2,6-bis[1 ,3-di-f
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with C 4 , C 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl and heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
  • R 11 and R 12 may be taken together with C 4 , C 5 and G 2 to form a ring;
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocar
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with C 4 , C 5 and G 2 to form a ring
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl;
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with C 4 , C 5 and G 2 to form a ring
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarby
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with C 4 , C 5 and G 2 to form a ring
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with E 2 , E 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • G 2 and C 5 may be connected by either a single bond or a double bond
  • G 2 and C 4 may be connected by either a single bond or a double bond
  • E 4 is selected from carbon, phosphorus and sulfur
  • X " is chloride, bromide, iodide, BF 4 " , PF 6 " , tosylate, mesylate, B(C 6 F 5 ) 4 " , 3,5-(C 6 H3)-(CF 3 )2 " or other common anions
  • i is 0 or 1
  • when i is 0, C 5 and C 4 may either not be connected by any bond, or may be connected by a single bond or a double bond
  • j is 0, 1 or 2
  • the carbon atoms between N 1 and E 4 are connected to each other by either single, double or triple bonds
  • m is 1 or 2 and is chosen to obey the valency of the
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with C 4 , C 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • R 10 and R 13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl
  • R 11 and R 12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl
  • R 11 and R 12 may be taken together with C 4 and C 5 and G 2 to form a ring
  • R 20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl
  • R 22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarby
  • M + is sodium, potassium, lithium or thallium cation; i is 0 or 1 when i is 0, C 5 and C 4 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N 1 and E 4 are connected to each other by either single, double or triple bonds; m is 1 or 2 and is chosen to obey the valency of the E 4 n is 0, 1 , 2 and is chosen to obey the valency of the C 4 and C 5 ; and g is 0, 1 , 2 and is chosen to obey the valency of C 2 .
  • E 10 in formulae II, III, XII and XII is nitrogen.
  • the compound are: N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- imine hydrochloride;
  • the invention provides a catalytic system comprising at least one compound according to any one of formulas I to XIX as defined above and a transition metal compound or complex.
  • the metal atom is a transition metal.
  • the metal is a Group 2-12 (lUPAC) transition metal or a lanthanide metal such as Ni, Pd, Pt, Fe, Co, Y, Ti, Zr, V, Hf, Cr, Mn, Ru, Rh, Re, Os, Ir, Cu, Mg, Zn and the rare earths (lanthanides).
  • Late transition metals are particularly preferred for coordination with the ligands of the invention in order to increase functional group tolerance.
  • the stoichiometric ratio of the compound to metal may range from 1 to 2, depending on the particular transition metal.
  • early transition metals which may be pentacoordinate or hexacoordinate, may have one or two ligands per metal atom respectively.
  • the ligand comprises an imine imidazole -2- imine scaffold A as shown in scheme (1) and its coordination to Titanium (IV) and Palladium (II).
  • the ligand structure is analogous to that of an amidine, where one of the nitrogen atoms is substituted with an imidazol-2-ylidene fragment. While not wishing to be bound by theory, it is believed that this aspect may be useful for further tailoring of the ligand electronics. This substitution effectively shifts the steric bulk from the first to the second coordination sphere, leading to a more open metal centre that is still protected from bimolecular decomposition.
  • Titanium (IV) complexes of the ligands of formula 3 can be synthesized by the
  • the coordination complexes include: N-(1 -(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine teterachlorotitanium(IV); N-(1 -(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-imine teterachlorotitanium(IV); /V-(1 -ethylimino-2,6-dimethylphenyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- iminedichloropalladium(ll
  • the present invention comprises a ligand as described herein as well precursors thereof and metal complexes using such ligands.
  • the invention also comprises, in another embodiment, processes utilizing the complexes of the invention.
  • processes include, but are not limited to, polymerization or copolymerization of monomers (particularly hetero-atoms-containing monomers such as acrylates, vinyl acetate and other vinyl monomer, as well as monomers such as lactides and lactones), cross-coupling reactions, hydroformylation, hydrogenation, hydrosylilation, and
  • the present invention has significant utility in the field of polymerization, in cross-coupling reactions, and in any catalytic transformations where four electron donor ligands are used.
  • One of the major issues with many known catalysts relates to the poisoning of the catalyst during use, which leads to a loss in activity of the catalyst and, therefore lower productivity of the desired product.
  • the present invention addresses this issue by incorporating a fragment on the ligand that has at least one mesomeric form that is zwitterionic, wherein one of the charges is localized on the donor atom, resulting in a partially negatively charged donor.
  • Filtrations of air and/or moisture-sensitive compounds were achieved by using modified stainless steel cannulae fitted with glass fiber filter discs at one end. All glassware and cannulae were dried overnight at 120 °C for 24 h before use. NMR spectra were recorded on a Bruker DRX 600 ( 1 H at 600 MHz, 13 C at 150.9 MHz), Bruker AV 400 ( 1 H at 400 MHz, 13 C at 100 MHz) or Bruker AV 300 ( 1 H at 300 MHz, 13 C at 75.5 MHz) spectrometer and are at room temperature unless otherwise stated.
  • reagents were purchased from Aldrich or Alfa Aesar, metal precursors from Strem (PdCI 2 ) or BDH (TiCI 4 ) and used as received unless otherwise stated.
  • IMes-HCI, 1 IPr-HCI, 1 IMes, 2 IPr, 2 imidazol-2-imine, 3 Pd(CH 3 CN) 2 CI 2 , 4 Pd(COD)CI 2 5 and TiCI 4 (THF) 2 6 were prepared using published procedures.
  • HMDS hexamethylenedisilazide (a.k.a. bis(trimethylsilyl)amide)
  • Example 1.1 W-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine hydrochloride; IMesN A lmine-HCI (3a)
  • Example 1.4 N-(1 -(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine; IMesN A lmine (Compound 1-1 b)
  • Example 1.12 Pyridine-2-6-bis[1 ,3-bis(2,4,6-trimethylphenyl)imidazolin- 2-methanaminium)] ditosylate, [(IMesN-CH 2 )2Py](OTs)2 (Compound I -5a)
  • Example 1.16 Sodium 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N- (2-phenylethenolate), Na[IMesN A ethenolate] (Compound Xl-1a)
  • Example 2.1 N-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine teterachlorotitanium(IV); Ti(IMesN A lmine)CI 4 (4a)
  • Reaction mixture was stirred for 2 h at room temperature and then filtered through a plug of CeliteTM. The solid was washed with benzene (1 mL) and the combined organic fractions were dried in vacuo for 30 min. The off-white solid was redissolved in benzene (3 mL) and added dropwise to a stirred solution of TiCI 4 (THF) 2 (86.9 mg, 0.260 mmol) in benzene (2 mL) at room temperature. The color of the reaction mixture changed to bright red from the original yellow solution. The reaction mixture was stirred for 45 min and the precipitated brick red solid was filtered, washed with benzene (2 x 3 mL), pentane (10 mL) and dried in vacuo.
  • THF TiCI 4
  • the color of the reaction mixture changed from the original yellow solution to orange brown.
  • the reaction mixture was further stirred for 2 h and the precipitated solid was filtered, washed with benzene (2 x 3 mL). Solid was dissolved in minimum amount of dichloromethane and the solution was passed through a plug of neutral alumina. The plug was washed with dichloromethane (1 mL) and the orange brown solution was added dropwise to stirred diethyl ether (10 mL). The product was isolated as yellow brown solid, which was dried dried under high vacuum for 12 h. Yield: 190 mg (76 %).
  • Example 2.7 Dichlorocyclopentadienyl-N-(4-Methylphenyl)-1 ,3- bis(mesityl)imidazol-2-iminecarboxamidotitanium(IV); CpTiCI 2 [IMesN(CO)N-p-tol]
  • CpTiCI 2 [IMesN(CO)N-p-tol] can also be prepared from IV-2b in an analogous manner.
  • Method A To a cold (-78 °C) suspension of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanaminium)]ditosylate (200 mg, 160 mmol) in THF ( 30 mL) was slowly added a solution of NaO f Bu (30 mg, 31 1 mmol) in THF (20 mL). The reaction mixture was slowly warmed to RT and then stirred for 4 h. The reaction mixture was filtered and then dried in vacuo for 3h.
  • Method B To a solution of CrCI 3 (THF) 3 (15 mg, 39 ⁇ ) in THF (1 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanamine (38 mg, 41 ⁇ ) at room temperature. The reaction mixture was stirred for overnight. The purple colour solution was filtered, evaporated to dryness and washed with pentane (2 x 3 mL) and dried.
  • Method A To a cold ( -78 °C) suspension of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanaminium)] ditosylate (170 mg, 135 mmol) in THF ( 20 mL) was slowly added a solution of NaOtBu (26 mg, 264 mmol) in THF (10 mL). The reaction mixture was slowly warmed to RT and then stirred for 4 h. The reaction mixture was filtered and then dried in vacuo for 3h.
  • Method B To a stirred solution of TiCU(THF) (18 mg, 48 umol) in THF (1 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanamine (47 mg, 52 ⁇ ) at room temperature. The reaction mixture was stirred for overnight. The grey colour solution was filtered, evaporated to dryness and washed with pentane (2 x 3 mL) and dried in vacuo to yield pale green solid.
  • Method A To a cold (-78 °C) suspension of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanaminium)] ditosylate (100 mg, 80 ⁇ ) in THF (10 mL) was slowly added a solution of NaO f Bu (15 mg, 155 mmol) in THF (10 mL). The reaction mixture was slowly warmed to RT and then stirred for 4 h. The reaction mixture was filtered and then dried in vacuo for 3 h.
  • Method B To a suspension of CrCI 2 (THF) 2 (14 mg, 52 ⁇ ) in THF (2 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanamine (50 mg, 55 ⁇ ) at room temperature and the reaction mixture was stirred for 20 h. The pale green solution was filtered, evaporated to dryness. The light green solid was washed with pentane (2 x 3 mL) and dried in vacuo.
  • Example 2.12 Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)]iron(ll) dichloride DI PP
  • Example 2.14 Bis(1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2- phenylethenolato))dichlorozirconium(IV); ZrCI 2 (lmesN A ethenolate) 2
  • Example 2.15 Cyclopentadienyl-1 ,3-bis(2,4,6-trimethylphenyl)imidazol- 2-imine-N-(2-phenylethenolatodichlorotitanium(IV) CpTiCI 2 (IMesN A ethenolate)
  • NCHCHN (me sityi)), 6.20 (s, 5H, Cp), 2.34 (s, 6H, p-CH 3 ⁇ mesm ), 2.26 (s, 12H,
  • Example 3 NMR and X-ray Crystal Studies of Ligands 3a and 3b and Coordination Complexes 4a and 5b.
  • the 1 H NMR (CDCI 3 ) spectrum for salt 3a shows characteristic resonances for the mesityl para- and ortho-CH 3 protons in a 1 :2 ratio at ⁇ 1.91 and 2.36, respectively.
  • a typical AX 2 spectrum for the isopropyl groups in 3b was observed as a set of two doublets at 5 1.12 and 1.06 integrating to 12 protons each and a septet at ⁇ 2.47 integrating to 4 protons, with vicinal coupling of 6.8 Hz observed for all three sets.
  • the angles between the best planes formed by the imidazole ring and each of the aryl rings at the 1 ,3-positions are 61.9°, 80.6° (3a) and 70.6°, 80.3° (3b).
  • the angles between the best planes formed by either the imidazole ring or the 2,6-dimethylphenyl group and that passing through C 1 , N 3 , C 4 , C 5 , N 4 , C 6 are 64.9°, 70.5° (3a) and 72.5°, 74.1 ° (3b), respectively. All the remaining bond lengths and angles are unexceptional and lie within the expected range.
  • the crystal structure for 4a ( Figure 2) shows a distorted octahedral geometry around the titanium(IV) centre.
  • the bond angles around the titanium atom are in the range of 60.50(12) °-177.72(5)°, with the smallest angle attributed to the amidine N 3 -Ti-N 4 bite angle.
  • the imine imidazol-2-imine ligand is coordinated in a monodentate fashion through N4, in further agreement with our previous observation through the amidinium salts 3a and 3b that the iminic nitrogen N 4 is more basic than N 3 .
  • the bond lengths between the palladium and bridging chloride ligands (2.3335(16) and 2.3413(18) A) are greater than between the metal centre and the terminal chloride CI2 (2.2920(18) A).
  • N 3 -C 4 bond in 5b at 1.321 (7) A is also slightly longer than that observed in the precursor salt (1.307(5) A).
  • the N3-C4 and C4-N 4 bond length of 1.321 (7) and 1.332(7) A in 5b are consistent with the coordination with palladium, which also results in a more acute C 4 -N 4 -C 6 bond angle of 1 18.8(5)° in 5b compared to 123.5(3)° observed for 3b.
  • the 2,6- diisopropylphenyl rings attached to N 1 and N 2 in 5b are approximately crystallographically equivalent due to a pseudo-mirror plane that is orthogonal to the imidazole ring and that passes through the exocyclic iminic bond.
  • the angles between the best plane passing through C 1 , N 3 , C 4 , C 5 , N 4 , C6 and those formed by the imidazole ring and the 2,6- dimethylphenyl group are 75.6° and 82.4°, respectively.
  • the plane passing through the bimetallic palladium bridge is tilted off by 65.8° from the best plane formed by N 3 , C 4 , C 5 , N 4 , C 6 .
  • N1-C2 N2-C3 1.382(2), 1.387(2) 1.396(4), 1.397(4) 1.397(5), 1.403(5) 1.386(5), 1.400(5) 1.395(7), 1.401(7)

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Abstract

The present invention relates to imine imidazole-2-imine molecules as ligands and their application in transition metal coordination complexes. The invention also relates to the use of said coordination compounds as catalysts in bond forming reactions such as polymerizations.

Description

CATALYST LIGANDS, CATALYTIC LIGAND COMPLEXES AND POLYMERIZATION PROCESSES USING SAME FIELD OF THE INVENTION [0001] The present invention relates to organic compounds as ligands, catalytic metal complexes formed with such ligands and the use of such catalysts in polymerization reactions and other bond forming reactions. BACKGROUND OF THE INVENTION [0002] Olefin polymers have a wide variety of industrial uses and are therefore economically important. The polymerization reactions used to form such polymers utilize catalysts, primarily comprising a metal and organic ligand complex. Research into polymerization catalysts has resulted in various improvements, which have made it possible to control polymerization processes and, thereby, control the physicochemical properties of the polymer products. [0003] Some of the catalysts developed for polymerization reactions are cationic. These cationic catalysts generally comprise neutral alpha-diimine ancillary ligands coordinated, or complexed with transition metals, in particular, late transition metals (i.e. a metal from Group 8-10). Examples of such cationic catalysts are provided Chem. Rev. 2000, 100(4), 1 169. Chem. Rev. 2003, 103(1), 283, Angew. Chem. Int. Ed. 1999, 38(4), 428, WO 96/23010, WO 98/27124, WO 02/22694, WO 10/14344, WO 98/49212. The use of late transition metals offers the possibility of using polar monomers, which is commercially significant since the mechanical properties of the resulting polymer/plastic/material could be much better controlled. However, these cationic catalysts, particularly when formed with transition metals such as titanium, zirconium and chromium, but even when formed with nickel or palladium have been found to have significant drawbacks when used in commercial operations due to the poisoning of the catalysts by the functionalized monomers used in the polymerization reaction. [0004] Another group of catalysts that has been proposed are charge neutral. These catalysts comprise an anionic ligand coordinated to late transition metals. Although such neutral catalysts have been found to be more tolerant of functional groups on monomers, they have also been found to be significantly less active than the cationic catalysts discussed above. Examples of such neutral catalysts are provided in Science 2000, 287(5452), 460, WO 01/92342, WO 01/68724. [0005] In addition to the use of nitrogen as a donor atom in ligands, its heavier congener phosphorus has also been used. In some reported cases, the use of a phosphine donor has led to enhanced thermal stability over the nitrogen analogue. This is thought to be due to the stronger metal-phosphorus bond strength, resulting in an increased binding constant. For example, Feringa (Chemical Communications 1998, 223-224) reported palladium phosphine imine catalysts that could oligomerize ethylene at 100 °C, well above temperatures at which the analogous alpha-diimine complexes, which contains a bidentate ligand with two nitrogen atoms as donor, would decompose (J. Am. Chem. Soc. 2000, 122, 6686 and Macromolecules 2000, 33, 2320). Similarly, Brookhart (Organometallics 2002, 21 (26), 5926-5934) reported the use of nickel phosphine imine catalyst for olefin polymerization with data that suggest enhanced thermal stability with long catalyst lifetime at 60 °C. [0006] Thus, in summary, cationic catalysts result in a desired degree of catalytic activity but suffer from being less tolerant to functional groups that are present on monomers (i.e. more prone to poisoning). Neutral catalysts, on the other hand, are more tolerant of monomer functional groups but are less active. As a solution to these issues, zwitterionic catalysts have also be proposed. An example of such zwitterionic catalyst is provided in US Publication number US 2002/0028741 and WO 2002/049758. [0007] There exists a need for an improved catalyst ligand for use in polymerization reactions that addresses at least some of the aforementioned deficiencies. In particular, there exists a need for a catalyst ligand being only partially negatively charged, in order to provide a ligand that balances the aforementioned characteristics of neutral and anionic ligands. SUMMARY OF THE INVENTION [0008] In one aspect, the present invention provides compound as ligands and precursors for use in a coordination complex. In a particular aspect of the invention there is provided a compound according to formula (I): (C2)j
/ \ /
12 \ a \
(R13)n (R22 'g (R20) 'im
I
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R21 is selected from hydrocarbyl, and substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R21 may be taken together with E4 and N2 to form a ring; when R20 and R21 together with E4 and N2 form a ring the ring may be further substituted with 1 to 4 substituents wherein the substituents are hydrocarbyl, substituted hydrocarbyl, heteroatom substituted hydrocarbyl or substituted heteroatom substituted hydrocarbyl and when the ring is substituted with a substituted heteroatom substituted hydrocarbyl, if the substitutent on the heteroatom substituted hydrocarbyl is C6.14 aryl, the substituent may be further substituted by up to 3 Ci-6 alkyl groups; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon and phosphorus; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2~ or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2. q is 0, 1 , or 2; and with the proviso that the compound is not 2,6-bis[1 ,3-di-fe/f-butylimidazolin-2- imino)methyl]pyridine. [0009] In another aspect of the invention there is provided a compound according to formula (II)
Figure imgf000007_0001
II wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl; R20 and R24 may be taken together with E4 and E10 to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; R23 and R24 can be taken together with E10 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected carbon; E5 is selected from carbon and boron; E10 is selected from nitrogen and phosphorus; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2~ or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 , or 2. In another aspect of the invention there is provided a compound according to formula (III):
Figure imgf000009_0001
HI
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R23 may be taken together with E4 and E10 to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is carbon; E5 is selected from carbon and boron; E10 is selected from nitrogen and phosphorus; E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when I is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1; m is 1 or 2 and is chosen to obey the valency of the E4 n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 , 2 and is chosen to obey the valency of C2. [0010] In another aspect of the invention there is provided a compound according to formula (IV):
Figure imgf000011_0001
IV wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl, R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R22 and R25 may be taken together with C2, C3 and E6 to form a ring; R25 and R23 may be taken together with E6, C3, and N2 to form a ring; R23 and R24 can be taken together with N2 to form a ring or a cycle; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted
hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E5 is selected from carbon and boron; E6 is selected from oxygen, sulfur and nitrogen; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2" or other common anions; i is 0 or 1 ; when i = 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 , or 2. [0011] In another aspect of the invention there is provided a compound according to formula (V):
Figure imgf000013_0001
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl, R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R23 and R25 may be taken together with N2, C3 and E6 to form a ring; R22 and R25 can be taken together with C2, C3 and E6 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E5 is selected from carbon and boron; E6 is selected from oxygen, sulfur and nitrogen; E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i = 0, E2 and E5 may either not be connected by any bond, or alternatively, may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 , 2 and is chosen to obey the valency of C2. [0012] In another aspect of the invention there is provided a compound according to formula (VI):
Figure imgf000015_0001
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R23 and R25 can be taken together with N2, C3 and E6 to form a ring; R22 and R25 may be taken together with C2, C3 and E6 to form a ring. G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E5 is selected from carbon and boron; E6 is selected from oxygen, sulfur and nitrogen; E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 , 2 and is chosen to obey the valency of C2. [0013] In another aspect of the invention there is provided a compound according to formula (VII):
q
Figure imgf000016_0001
VII wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted
hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon, phosphorus and sulfur; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2" or other common anions; i is 0 or 1 when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2. [0014] In another aspect of the invention there is provided a compound according to formula (VIII):
Figure imgf000018_0001
VIII wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl; R20 and R24 may be taken together with E4 and O to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted
hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon and phosphorus; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ~, 3,5-(C6H3)-(CF3)2 " or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2. [0015] In another aspect of the invention there is provided a compound according to formula (IX):
Figure imgf000020_0001
:
IX
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon and phosphorus; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when I is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4 n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 , 2 and is chosen to obey the valency of C2. [0016] In a further aspect of the invention there is provided a catalytic system comprising at least one compound according to any one of formulas I to IX as defined above and a transition metal compound or complex. [0017] A further aspect of the invention is the utility of the catalytic system to catalyze bond forming reactions including polymerization, copolymerization, cross-coupling reactions, hydroformylation, hydrogenation, hydrosilylation and hydroboration. BRIEF DESCRIPTION OF THE DRAWINGS [0018] The features of the invention will become more apparent in the following detailed description in which reference is made to the appended drawings wherein: [0019] Figure 1 shows the solid state molecular structure of amidinium salts 3a and 3b determined by single crystal X-ray diffraction studies. Thermal ellipsoids are drawn at 40% probability. Hydrogen atoms and solvent molecules (CH2CI2) are omitted for clarity. [0020] Figure 2 shows the solid state molecular structure of 4a as determined by single crystal X-ray diffraction studies. Thermal ellipsoids are drawn at 40% probability. Hydrogen atoms and solvent molecule (CHCI3) have been removed for clarity. [0021] Figure 3 shows the solid state molecular structure of 5a as determined by single crystal X-ray diffraction studies. Thermal ellipsoids are drawn at 40% probability. Hydrogen atoms and solvent molecule (CH2CI2) have been removed for clarity. DETAILED DESCRIPTION OF THE INVENTION [0022] As used herein, the term "polymerization" refers to a process wherein at least two olefin molecules are combined into a single molecule ("dimerized"), or an oligomer or polymer is formed. Preferably the average degree of polymerization (DP, the average number of monomer units in the product molecules) is 5 or more, more preferably about 10 more, and especially preferably about 25 or more. [0023] As used herein, the term "polymer" refers to a species comprised of monomer units and having a degree of polymerization (DP) of 10 or higher. [0024] As used herein, the terms "monomer" or "olefin monomer" refer to the olefin or other monomer compound before it has been polymerized. [0025] As used herein the term "monomer units" refers to the monomer moieties that are combined together to form a polymer, after they have been polymerized. [0026] As used herein the term "Ngand" refers to an ionic or neutral molecule that binds to a central metal atom to form a coordination complex. [0027] Symbols ordinarily used to denote elements in the Periodic Table take their ordinary meaning, unless otherwise specified. Thus, C, H, N, O, S, P, and Si stand for carbon, hydrogen, nitrogen, oxygen, sulfur, phosphorus and silicon, respectively.
Furthermore the symbols C1 to C5 as used herein represent carbon atoms and are numbered for ease of reference, similarly N1 and N2 represent nitrogen atoms and are numbered for ease of reference. [0028] As used herein the term "hydrocarbyl" means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms, and may be saturated or unsaturated. Examples of monovalent hydrocarbyls include the following: C1 -C20alkyl; C3 -C8 cycloalkyl or C6-C14 aryl. Cyclic hydrocarbyls may include mono or multiclyclic ring systems. Examples of divalent (bridging hydrocarbyls) include: --CH2 -, ~ CH2CH2 -, -C6H4 -, and -CH2CH2CH2 -. [0029] As used herein the term "substituted hydrocarbyl" refers to a hydrocarbyl substituted with one or more groups selected from C C20 alkyl, C3 -C8 cycloalkyl or C6-C14 aryl; In an embodiment the substituted hydrocarbyl includes one to four substituents as described above. [0030] As used herein, the term "aryl" refers to an aromatic group having 6 to 14 carbon atoms. Examples of aryl groups include phenyl, naphthyl, and anthracenyl groups. Aryl may also refer to a cyclic aromatic group having 5 to 14 members if one or more of the members are heteroatoms selected from O, N and S. [0031] A "heteroatom" refers to an atom other than carbon or hydrogen. Examples of heteroatoms include oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, silicon, chlorine, bromine, and fluorine. [0032] A "heteroatom substituted hydrocarbyl" refers to i) a monovalent or divalent hydrocarbyl substituted with one or more heteroatoms. Examples of monovalent heteroatom substituted hydrocarbyls include: trifluoromethyl, 2,6- dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4- methoxycarbonyl-2,6-dimethylphenyl. 2-tert-butyl-6-chlorophenyl, 2,6-dimethyl-4- phenylsulfonylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6-dimethyl-4-trifluoromethylphenyl, 2,6- dimethyl-4-trimethylammoniumphenyl (associated with a weakly coordinating anion), 2,6- dimethyl-4-hydroxyphenyl, 9-hydroxyanthr-10-yl, 2-chloronapth-1 -yl, 4-methoxyphenyl, 4- nitrophenyl, and 9-nitroanthr-10-yl. Examples of divalent heteroatom substituted
hydrocarbyls include 4-methoxy-1 ,2-phenylene, 1-methoxymethyl-1 ,2-ethanediyl, 1 ,2- bis(benzyloxymethyl)-1 ,2-ethanediyl, and 1-(4-methoxyphenyl)-1 ,2-ethanediyl; ii) a C C20 alkyl wherein from 1 to 6 carbon atoms are replaced with heteroatoms selected from oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, silicon and/or wherein 1-12 of the hydrogens atoms are replaced with chlorine, bromine, and/or fluorine and wherein the the number of carbon and/or hydrogen atoms replaced will be suitably selected based on the number of carbon and hydrogen atoms in the alkyl chain; iii) a C3 -C8 cycloalkyl wherein from 1 to 4 carbon atoms are replaced with heteroatoms selected from oxygen, nitrogen, sulfur, and/or wherein 1-8 of the hydrogens atoms are replaced with chlorine, bromine, and/or fluorine and wherein the number of carbon and/or hydrogen atoms replaced will be suitably selected based on the number of carbon and hydrogen atoms in the cycloalkyl ring; or iv) a C5-C14 aryl wherein from 2 to 4 carbon atoms are replaced with heteroatoms selected from oxygen, nitrogen, sulphur and/or wherein 1-8 hydrogen atoms are replaced with chlorine, bromine, and/or fluorine and wherein the number of carbon and/or hydrogen atoms replaced with be suitably selected based on the number of carbon and hydrogen atoms in the aryl ring; and heteroatom substituted hydrocarbyl may further include a combination of up to two of ii), iii) and iv) as defined above. Further examples of monovalent and divalent heteroatom substituted hydrocarbyls and hydroaryls include: methoxymethyl, diphenylphosphinemethyl, 2-furyl, 3-furyl, 2-pyridinyl, 3- pyridinyl, 4-pyridinyl, 2-thiophenyl, 3-thiophenyl, 2-oxazolyl, 4-imidazolyl, 4-imidazolidinyl, 2- imidazolidinyl, 2,3-dihydrobenzimidazol-2-yl, 2-piperidinyl, phenoxymethyl, tetrahydropyran- 2,6-diyl, 1 '-ethoxyethane-2,2'-diyl, and derivatives thereof. [0033] As used herein the term "substituted heteroatom substituted hydrocarbyl" refers to a heteroatom substituted hydrocarbyl that is further substituted with one or more groups selected from C C2o alkyl, C3 -C8 cycloalkyl or C6-C14 aryl; In an embodiment the substituted heteroatom substituted hydrocarbyl includes one to four substituents as described above. [0034] As used herein the term "heteroatom attached hydrocarbyl" refers to a hydrocarbyl group that is attached or bound to a heteroatom that is in turn attached or bound to the remainder of the molecule. Examples of heteroatom attached hydrocarbyl include: methoxy (OCH3), ethoxy (OCH2CH3), phenoxy (0(C6H5), dimethylamine (N(CH3)2), diphenylphosphine (P(C6H5)2). Similarly the terms "heteroatom attached substituted hydrocarbyl", "heteroatom attached heteroatom substituted hydrocarbyl" and "heteroatom attached substituted heteroatom substituted hydrocarbyl" refer to a substituted hydrocarbyl or to a heteroatom substituted hydrocarbyl, or to a substituted heteroatom substituted hydrocarbyl respectively, as defined above, that is attached or bound to a heteroatom that is in turn attached or bound to the remainder of the molecule. [0035] As used herein the terms "silicon-attached hydrocarbyl" and "tin-attached hydrocarbyl" refer to a hydrocarbyl group that is attached or bound to a silicon or tin atom respectively, and the silicon or tin atom is in turn attached or bound to the remainder of the molecule. [0036] The present invention is based upon the development of a new ligand scaffold that has a fragment and that, by nature of its chemical composition, can adopt at least one mesomeric (resonance) form that is zwitterionic. As known in the art, zwitterions are molecules that have both a formal positive and negative charge on different atoms within the molecules, but with a net or overall charge of zero. Thus, zwitterions are overall neutral. The invention takes advantage of the mesomeric characteristic, resulting in one of the possible donor atoms involved in coordinating to a metal centre, namely N1, being overall partially negatively charged by nature of the possible mesomeric structures, some of which would lead to a formally negative charge on one of the donor atoms and some of which would lead to a neutral (zero) charge on that same donor atom. [0037] On average, one of the potential donor atoms on the ligand, namely N1, would only bear a partial negative charge, thus conferring some unique properties to the ligand of the invention. The partially negatively charged donor atom on the ligands of the invention results in metal catalyst active centres that are relatively electron rich and less electrophilic compared to a system where the partially negatively charged donor atom is replaced by a neutral donor atom. The catalysts of the invention will therefore undergo oxidative addition, and migratory insertion into carbon monoxide and olefins more readily. This results, in many cases, in catalysts that are more active and more productive. The decrease in the electrophilicity of the metal centre also mitigates and even eliminates the potential of the catalyst being poisoned by a Lewis base (e.g. a monomer having a functional group that functions as a Lewis base). As discussed above, such poisoning was found to be a severe limitation of other known systems. Thus, the invention makes it possible to conduct reactions between the metal complexes coordinated by the ligands disclosed herein and substrates containing functional groups (e.g. functionalized olefins, such as acrylates). For example, when coordinated to late transition metals, the metal complexes coordinated by the ligands of the invention may be used to polymerize functional group containing vinyl monomers. As a further example, when coordinated to early transition metals, the metal complexes coordinated by the ligands of the invention may be used to polymerize olefins in the presence of less expensive cocatalysts. In such cases, the partially negatively charged donor of the ligand of the invention allows for a balance between the activity of the catalyst and the tolerance of functional groups. [0038] Thus, in one aspect, the olefin polymerization catalysts of the present invention comprise transition metal complexes of bidentate ligands with said bidentate ligand being comprised of a fragment that is zwitterionic where one of the possible donor atoms, N1, bears a partially negative charge due to the possible mesomeric structures. [0039] In one aspect, the invention provides a compound of formula (I):
Figure imgf000026_0001
I
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R21 is selected from hydrocarbyl, and substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R21 may be taken together with E4 and N2 to form a ring; when R20 and R21 together with E4 and N2 form a ring the ring may be further substituted with 1 to 4 substituents wherein the substituents are hydrocarbyl, substituted hydrocarbyl, heteroatom substituted hydrocarbyl or substituted heteroatom substituted hydrocarbyl, and when the ring is substituted with a substituted heteroatom substituted hydrocarbyl, if the substitutent on the heteroatom substituted hydrocarbyl is C6.14 aryl, the substituent may be further substituted by up to 3 Ci-6 alkyl groups;
R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon and phosphorus; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2~ or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the cabon atoms between N1 and E4 are connected to each other by single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 or 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2; and with the proviso that the compound is not 2,6-bis[1 ,3-di-fe/f-butylimidazolin-2- imino)methyl]pyridine. [0040] In another aspect, the invention provides a compound of formula (II):
Figure imgf000029_0001
II wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl; R20 and R24 may be taken together with E4 and E10 to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; R23 and R24 can be taken together with E10 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is carbon; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; E10 is selected from nitrogen and phosphorous X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2~ or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 or 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2. [0041] In another aspect, the invention provides a molecule of formula (III):
Figure imgf000031_0001
III wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R23 may be taken together with E4 and E10 to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is carbon; E5 is selected from carbon and boron; E10 is selected from nitrogen and phosphorous; E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0, 1 or 2; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; When j is 2 the carbon atoms between N1 and E4 are connected to each other by either single double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 or 2 and is chosen to obey the valency of C2. [0042] In another aspect, the invention provides a compound of formula (IV):
Figure imgf000033_0001
IV wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R22 and R25 may be taken together with C2 , C3 and E6 to form a ring; R25 and R23 can be taken together with E6, C3 and N2 to form a ring; R23 and R24 can be taken together with N2 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted
hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E5 is selected from carbon and boron; E6 is selected from oxygen, sulfur and nitrogen; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2" or other common anions; i is 0 or 1 ; when i = 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; When j is 2 the carbon atoms between N1 and E4 are connected to each other by either single double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 or 2 and is chosen t obey the valency of C2; and q is 0, 1 or 2. In another aspect, the invention provides a compound of formula (V):
Figure imgf000035_0001
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R23 and R25 can be taken together with N2, C3 and E6 to form a ring; R22 and R25 can be taken together with C2, C3 and E6 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E5 is selected from carbon and boron; E6 is selected from oxygen, sulfur and nitrogen; E2 and E3 may be connected by a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i = 0, E2 and E5 may either not be connected by any bond, or alternatively, may be connected by a single bond or a double bond; j is 0, 1 or 2; When j is 2 the carbon atoms between N1 and E4 are connected to each other by either single double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 or 2 and is chosen to obey the valency of C2. [0043] In another aspect, the invention provides a compound of formula (VI):
Figure imgf000036_0001
VI wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R23 and R25 can be taken together with N2, C3 and E6 to form a ring; R22 and R25 can be taken together with C2, C3 and E6 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E5 is selected from carbon and boron; E6 is selected from oxygen, sulfur and nitrogen; E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; When j is 2 the carbon atoms between N1 and E4 are connected to each other by either single double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 or 2 and is chosen to obey the valency of C2. [0044] In another aspect of the invention there is provided a compound according to formula (VII):
Figure imgf000038_0001
VII wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted
hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon, phosphorus and sulfur; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ~, 3,5-(C6H3)-(CF3)2" or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2. [0045] In another aspect of the invention there is provided a compound according to formula (VIII):
Figure imgf000040_0001
VIII wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl; R20 and R24 may be taken together with E4 and O to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted
hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon and phosphorus; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ~, 3,5-(C6H3)-(CF3)2" or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2. [0046] In another aspect of the invention there is provided a compound according to formula (IX):
Figure imgf000042_0001
ix
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and E2 may be connected by either a single bond or a double bond; G2 and E5 may be connected by either a single bond or a double bond; E1 is selected from nitrogen, oxygen and sulfur E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon and phosphorus; E5 is selected from carbon and boron; E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of the E1 ; m is 1 or 2 and is chosen to obey the valency of the E4 n is 0, 1 , 2 and is chosen to obey the valency of the E2, E3 and E5; and g is 0, 1 , 2 and is chosen to obey the valency of C2. [0047] With respect to formulae I to IX it will be understood by a person of skill in the art that in the case where j is 0 there is no C2 atom and therefore there is also no substituent group R22. [0048] In an embodiment of the invention the compounds of formulae I to IX are suitable for use as ligands or ligand precursors. [0049] In a further embodiment E2 of formulae l-IX is carbon. In a further embodiment E5 of formulae l-IX is carbon. In a further embodiment E1 of formulae l-IX is nitrogen. In a further embodiment E3 of formulae l-IX is nitrogen. In still a further embodiment in the formulae l-IX E2 and E5 are carbon and E1 and E3 are nitrogen. [0050] In an embodiment of the invention there is provided a compound of the formula XI:
Figure imgf000044_0001
XI
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4, C5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R21 is selected from hydrocarbyl, and substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R21 may be taken together with E4 and N2 to form a ring; when R20 and R21 together with E4 and N2 to form a ring the ring may be further substituted with 1 to 4 substituents wherein the substituents are hydrocarbyl, substituted hydrocarbyl, heteroatom substituted hydrocarbyl or substituted heteroatomsubstituted hydrocarbyl and when the ring is substituted with a substituted heteroatom substituted hydrocarbyl if the substitutent on the heteroatom substituted hydrocarbyl is C6.14 aryl the substituent may be further substituted by up to 3 C1-6 alkyl groups; R20 and R22 may be taken together with C2 and E4 to form a ring; E4 is selected from carbon and phosphorus; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, or other common anions; i is 0, in which case C4 and C5 may either not be connected by any bond, or alternatively, may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; g is 0, 1 , 2 and is chosen to obey the valency of C2; k is O, 1 or 2; m is 1 or 2 and is chosen to obey the valency of the E4; and with the proviso that the compound is not 2,6-bis[1 ,3-di-fe/f-butylimidazolin-2- imino)methyl]pyridine. [0051] In a further embodiment there is provided a compound of the formula XII:
Figure imgf000046_0001
XII wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4, C5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl and tin-attached hydrocarbyl; R20 and R24 may be taken together with E4 and E10 to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; E4 is carbon; E10 is selected from nitrogen and phosphorus; X is chloride, bromide, iodide, BF4 , PF6 , tosylate, mesylate, or other common anions; i is 0, in which case C4 and C5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; g is 0, 1 , 2 and is chosen to obey the valency of C2; k is O, 1 or 2; and m is 1 or 2 and is chosen to obey the valency of the E4. [0052] In a further embodiment there is provided a compound of the formula XIII:
Figure imgf000047_0001
XIII R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4, C5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring; R20 and R23 may be taken together with E10 and E4 to form a ring; E4 is carbon; E10 is selected from nitrogen and phosphorus; M+ is sodium, potassium, lithium or thallium cation; i is 0, in which case C4 and C5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by single, double or triple bonds; g is 0, 1 , 2 and is chosen to obey the valency of C2; and m is 1 or 2 and is chosen to obey the valency of the E4. [0053] In a further embodiment there is provided a compound of the formula XIV:
Figure imgf000048_0001
XIV wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4, C5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl and tin-attached hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl and heteroatom-substituted hydrocarbyl; R22 and R25 may be taken together with C2, C3 and E6 to form a ring; R24 and R25 can be taken together with N2, C3 and E6 to form a ring; E6 is selected from oxygen, sulfur and nitrogen; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, or other common anions; i is 0, in which case C4 and C5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; g is 0, 1 , 2 and is chosen to obey the valency of C2; k is 0 or 1 and is chosen to obey the valency of the E6 q is 0, 1 or 2. [0054] In a further embodiment there is provided a compound of the formula XV:
Figure imgf000050_0001
XV wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4, C5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 and R25 may be taken together with C2, C3 and E6 to form a ring; R23 and R25 may be taken together with N2, C3 and E6 to form a ring; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; E6 is selected from oxygen, sulfur and nitrogen; M+ is sodium, potassium, lithium or thallium cation; i is 0, in which case C4 and C5 may either not be connected by any bond, or alternatively, may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; g is 0, 1 , 2 and is chosen to obey the valency of C2; k is 0 or 1 and is chosen to obey the valency of E6. [0055] In a further embodiment there is provided a compound of the formula XVI:
Figure imgf000051_0001
xvi
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4, C5 and G2 to form a ring; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl; R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R22 and R25 may be taken together with C2, C3 and E6 to form a ring; R23 and R25 may be taken together with N2, C3 and E6 to form a ring; E6 is selected from oxygen, sulfur and nitrogen; M+ is sodium, potassium, lithium or thallium cation; i is 0, in which case C4 and C5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; g is 0, 1 , 2 and is chosen to obey the valency of C2; and k = 0 or 1 and is chosen to obey the valency of the E6.
[0056] In a further embodiment there is provided a compound of the formula XVII:
Figure imgf000052_0001
xvii
wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with E2, E5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted
hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and C5 may be connected by either a single bond or a double bond; G2 and C4 may be connected by either a single bond or a double bond; E4 is selected from carbon, phosphorus and sulfur; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2" or other common anions; i is 0 or 1 ; when i is 0, C5 and C4 may either not be connected by any bond, or may be connected by a single bond or a double bond j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the C5, and C4; g is 0, 1 or 2 and is chosen to obey the valency of C2; k is 0, 1 , or 2. [0057] In a further embodiment there is provided a compound of the formula XVIII:
Figure imgf000054_0001
XVIII wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4, C5 and G2 to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl; R20 and R24 may be taken together with E4 and O to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and C5 may be connected by either a single bond or a double bond; G2 and C4 may be connected by either a single bond or a double bond; E4 is selected from carbon and phosphorus; X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)-(CF3)2~ or other common anions; i is 0 or 1 ; when i is 0, C5 and C4 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds' m is 1 or 2 and is chosen to obey the valency of the E4; n is 0, 1 , 2 and is chosen to obey the valency of the C4 and C5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and k is O, 1 or 2. [0058] In a further embodiment there is provided a compound of the formula XIX:
Figure imgf000056_0001
XIX wherein, R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R11 and R12 may be taken together with C4 and C5 and G2to form a ring; R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom- substituted hydrocarbyl; R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom- substituted hydrocarbyl; G2 and C5 may be connected by either a single bond or a double bond; G2 and C4 may be connected by either a single bond or a double bond; E4 is selected from carbon and phosphorus;
M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 when i is 0, C5 and C4 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; m is 1 or 2 and is chosen to obey the valency of the E4 n is 0, 1 , 2 and is chosen to obey the valency of the C4 and C5; and g is 0, 1 , 2 and is chosen to obey the valency of C2. [0059] In a further embodiment E10 in formulae II, III, XII and XII is nitrogen. [0060] In yet a further embodiment the compound are: N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- imine hydrochloride;
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2- imine hydrochloride;
N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-di-tert-butylimidazol-2-imine hydrochloride;
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- imine;
N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2- imine;
N-(2-iodo-1-(4-chlorophenyl)ethylidene)-2,4,6-trimethylaniline;
N-(2-(mesitylimino)-2-(4-chlorophenyl)ethyl))-1 ,3-bis(2,4,6-trimethylphen- yl)imidazol-2-imine hydroiodide;
N-(4-Methylphenyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2- iminecarboxamide;m;
N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarboxamide;
N-(4-Methylphenyl)-N-trimethylsilyl-1 ,3-bis(mesityl)imidazol-2-iminecarboxamide; Lithium N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarboxamide; Pyridine-2-6-bis[1 ,3-bis(2,4,6-trimethylphenyl)imidazolin-2-methanami ditosylate; Pyridine-2-6-bis[1 ,3-bis(2,6-diisopropylphenyl)imidazolin-2- methanaminium)] ditosylate;
N-(2-oxo-2-phenylethyl))-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine hydrobromide;
N-(2-oxo-2-phenylethyl))-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine or Sodium 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2-phenylethenolate). [0061] In another aspect of the invention there is provided the use of a compound as defined in formulae l-XIX as ligands or ligand precursors. [0062] In another aspect, the invention provides a catalytic system comprising at least one compound according to any one of formulas I to XIX as defined above and a transition metal compound or complex. In a further aspect the metal atom is a transition metal. In particular, the metal is a Group 2-12 (lUPAC) transition metal or a lanthanide metal such as Ni, Pd, Pt, Fe, Co, Y, Ti, Zr, V, Hf, Cr, Mn, Ru, Rh, Re, Os, Ir, Cu, Mg, Zn and the rare earths (lanthanides). Late transition metals are particularly preferred for coordination with the ligands of the invention in order to increase functional group tolerance. [0063] The stoichiometric ratio of the compound to metal may range from 1 to 2, depending on the particular transition metal. For example, early transition metals which may be pentacoordinate or hexacoordinate, may have one or two ligands per metal atom respectively. [0064] In one aspect of the invention the ligand comprises an imine imidazole -2- imine scaffold A as shown in scheme (1) and its coordination to Titanium (IV) and Palladium (II). The ligand structure is analogous to that of an amidine, where one of the nitrogen atoms is substituted with an imidazol-2-ylidene fragment. While not wishing to be bound by theory, it is believed that this aspect may be useful for further tailoring of the ligand electronics. This substitution effectively shifts the steric bulk from the first to the second coordination sphere, leading to a more open metal centre that is still protected from bimolecular decomposition.
Figure imgf000059_0001
2 Scheme 1 : Mesomeric structures for imine imidazol-2-imine ligands
3 [0065] This ligand takes advantage of the various possible mesomeric structures,
4 including two distinct zwitterionic isomers B and C (Scheme 1). Thus, although the ligand is
5 overall neutral, both exocyclic nitrogen atoms are electron-rich from the delocalised negative
6 charge as shown in D (Scheme 1). Coordination of these electron-rich ligands should thus
7 lead to transition metal centres with decreased electrophilicity.
8 [0066] Compounds of the general formula A as shown in Scheme 1 can be prepared
9 by the reaction of an imidazol-2-imine of formula 1 with imidoyl chloride of formula 2 in
10 toluene (125 °C) for 12 h as shown in Scheme 2.
Figure imgf000059_0002
12 Scheme 2
13 [0067] Titanium (IV) complexes of the ligands of formula 3 can be synthesized by the
14 reaction of (THF)TiCI4with the neutral ligand generated in situ by deprotonation of the
15 corresponding hydrochloride salt, N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-
16 trimethylphenyl)imidazol-2-imine hydrochloride (3a) and N-(1-(2,6-
17 dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-imine hydrochloride
18 (3b), in benzene as shown in Scheme 3. Reaction of the in situ generated free ligand with
19 (CH3CN)2PdCI2 in benzene at room temperature over 2 h produced the palladium (II)
20 complexes. 3 a,b
Figure imgf000060_0001
Scheme 3 [0068] Although the ligands can bind to metals in a bidentate fashion, it will be understood that systems in which the ligands bind in a monodentate fashion to the metal centers are also included. [0069] In an embodiment the coordination complexes include: N-(1 -(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine teterachlorotitanium(IV); N-(1 -(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-imine teterachlorotitanium(IV); /V-(1 -ethylimino-2,6-dimethylphenyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- iminedichloropalladium(ll) dimer;
N-(1 -(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-imine dichloropalladium(ll) dimmer; /V-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine)- ferf-butylimidodichlorotitanium(IV); N-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine)- (2-tert-butylphenylimido)dichlorotitanium(IV); Dichlorocyclopentadienyl-N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarbox- amidotitanium(IV); Dichlorobis-N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarboxam titanium(IV); Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-methanamine)] chromium(lll) trichloride; Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-methanamine)]titanium trichloride; Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)]chromium(ll) dichloride; Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-methanamine)]iron(ll) dichloride; Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-methanamine)]cobalt(ll) dichloride; or Bis(1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2- phenylethenolato))dichlorozirconium(IV); Cyclopentadienyl-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2- phenylethenolatodichlorotitanium(IV);
[0070] In one aspect, the present invention comprises a ligand as described herein as well precursors thereof and metal complexes using such ligands. The invention also comprises, in another embodiment, processes utilizing the complexes of the invention. For example, such processes include, but are not limited to, polymerization or copolymerization of monomers (particularly hetero-atoms-containing monomers such as acrylates, vinyl acetate and other vinyl monomer, as well as monomers such as lactides and lactones), cross-coupling reactions, hydroformylation, hydrogenation, hydrosylilation, and
hydroboration. [0071] The present invention has significant utility in the field of polymerization, in cross-coupling reactions, and in any catalytic transformations where four electron donor ligands are used. One of the major issues with many known catalysts relates to the poisoning of the catalyst during use, which leads to a loss in activity of the catalyst and, therefore lower productivity of the desired product. The present invention addresses this issue by incorporating a fragment on the ligand that has at least one mesomeric form that is zwitterionic, wherein one of the charges is localized on the donor atom, resulting in a partially negatively charged donor. EXAMPLES [0072] Other features of the invention will become apparent in the course of the following description of the exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof. General procedures [0073] All manipulations of air and/or moisture sensitive materials were carried out under an inert atmosphere of dinitrogen using standard Schlenk vessel techniques, or in an inert-atmosphere glove box containing dinitrogen. Dinitrogen was purified by passage through columns filled with molecular sieves (4 A) and manganese (II) oxide suspended on vermiculite for the vacuum line. All solvents were dried by refluxing and then distilling over sodium (pentane, toluene, diethylether and THF) or CaH2 (dichloromethane, CH3CN and chloroform) under a positive pressure of dinitrogen and deoxygenated by bubbling dry dinitrogen through the dried solvents for twenty minutes before use. Solvents and solutions were transferred through stainless steel cannulae using a positive pressure of dinitrogen. Deuterated solvents were degassed using three freeze-pump-thaw cycles and were vacuum distilled over sodium (C6D6 and toluene) or CaH2 (CDCI3, CD2CI2 and CD3CN) and stored in the glove box. Filtrations of air and/or moisture-sensitive compounds were achieved by using modified stainless steel cannulae fitted with glass fiber filter discs at one end. All glassware and cannulae were dried overnight at 120 °C for 24 h before use. NMR spectra were recorded on a Bruker DRX 600 (1H at 600 MHz, 13C at 150.9 MHz), Bruker AV 400 (1H at 400 MHz, 13C at 100 MHz) or Bruker AV 300 (1H at 300 MHz, 13C at 75.5 MHz) spectrometer and are at room temperature unless otherwise stated. The spectra were referenced internally relative to the residual protio-solvent (1H) and solvent (13C) resonances and chemical shifts were reported with respect to δ = 0 for tetramethylsilane. Microanalyses were performed either by ANALEST of the Department of Chemistry, University of Toronto or by Guelph Chemical Laboratories LTD, Guelph, Ontario, Canada, N1 G 5G5. Exact masses were determined by the AIMS Laboratory, Department of Chemistry, University of Toronto or microanalytical laboratory of the Department of Chemistry, McMaster University. [0074] All reagents were purchased from Aldrich or Alfa Aesar, metal precursors from Strem (PdCI2) or BDH (TiCI4) and used as received unless otherwise stated. IMes-HCI,1 IPr-HCI,1 IMes,2 IPr,2 imidazol-2-imine,3 Pd(CH3CN)2CI2,4 Pd(COD)CI2 5 and TiCI4(THF)2 6 were prepared using published procedures. /V-(2,6-Dimethylphenyl)acetimidoyl chloride was prepared by heating the starting amide and phosphorus pentachloride under vacuum in the absence of solvent7 and the 1H NMR data was compared with the literature.8 NaOfBu was sublimed and kept in an inert-atmosphere glove box. [0075] Abbreviations: mesityl
'Bu tertiary-butyl p-tol para-tolyl
Me methyl
Mes mesityl
DIPP 2,6-diisopropylphenyl
COD cyclooctadiene
THF tetrahydrofuran
py pyridine
TMEDA tetramethylethylene diamine
HMDS hexamethylenedisilazide (a.k.a. bis(trimethylsilyl)amide)
Cp cyclopentadienyl
OTs toluene sulfonate
FTIR Fourier-Transform Infrared
HRMS High-resolution mass spectrometry
NMR Nuclear magnetic resonance
s singlet
d doublet
t triplet
DIPP diisopropylphenyl
Example 1 : Synthesis of Ligand Precursors
[0076] Example 1.1: W-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine hydrochloride; IMesNAlmine-HCI (3a)
Figure imgf000064_0001
[0077] A solution of 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine IMesNH (6.58 g, 20.60 mmol) in toluene (50 mL) was slowly added to a solution of Λ/-(2,6- dimethylphenyl)acetimidoyl chloride (3.63 g, 20.0 mmol) in toluene (20 mL) at room temperature. The reaction mixture was heated to reflux at 125 °C for 16 h and then cooled to room temperature. The off-white solid was filtered, washed with toluene (20 mL), diethylether (2 x 20 mL) and dried in vacuo. Yield 7.2 g (93 %). Crystals suitable for X-ray diffraction were grown by layering pentane over a saturated dichloromethane solution. [0078] 1H NMR (400 MHz, CDCI3): δ 1 1.2 (s, 1 H, NH(imine)), 6.98 (s, 4H, m- CH(mesityi)) , 6.95 (br t, 1 H, 3J = 8.0 Hz, p-CH(2,6-xyiyi)) , 6.90 (s, 2H, -NCHCHN-), 6.84 (d, 2H, 3 J = 7.7 Hz, m-CH(2 6-Xyiyi)) , 2.36 (s, 6H, p-C/~/3(meSityi)) , 2.1 1 (s, 3H, CH3^imme ), 1.92 (s, 12H, o- C/-/3(mesityl)) , 1 -60 (S, 6H, 0-C/-/3(2,6-xylyl)) - [0079] 13C{1H) NMR (100.6 MHz, CDCI3): δ 162.3 (s, -NC(imine)N-), 146.8 (s, - NCf,m,dazo/m;N-), 140.6 (s, C{mesm), 135.6 (s, o-C(meSityi)) , 135.1 (s, C(2,6-xyiyi)) , 134.6 (s, o-C(2,6- xylyl)), 129.9 (s, p-C(mesityi)) , 129.8 (s, m-CH(meSityi)) , 127.0 (s, m-CH(2,6-xyiyi)) , 127.1 (s, p-CH(2,6- xylyl)), 1 18.9 (s, -NCHCHN-), 21.0 (s, p-CH3(mesityi)) , 9-7 (s, CH3(im ine)) , 17.6 (s, o-CH3(mesityi)) , 17.5 (S, 0-CH3(2,6-xylyl)) [0080] Anal. Calcd. For C31H37CIN4 (%): C, 74.45; H, 7.26; N, 1 1.20; Found (%): C, 72.81 ; H, 7.26; N, 10.98. Multiple microcombustion analyses always gave lower C contents. [0081] High Resolution Mass Spectrometry (HRMS) (ESI CH3CN): Calculated for C31 H37CIN4, m/z = 464.2940 [M-CI]+; Found: 464.2946 [M-CI]+ [0082] Fourier Transform Infrared (FTIR) (Thin film): vc=N 1617 cm"1 , vc=c 1519 cm"1 [0083] Example 1.2: W-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,6- diisopropylphenyl)imidazol-2-imine hydrochloride, IPrNAlmine HCI (Compound I -2a) (3b)
Figure imgf000065_0001
[0084] A solution of 1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-imine IPrNH (6.33 g, 15.68 mmol) in toluene (70 mL) was slowly added to a solution of N-(2,6- dimethylphenyl)acetimidoyl chloride (2.71 g, 14.9 mmol) in toluene (20 mL) at room temperature. The reaction mixture was heated to reflux at 125 °C for 12 h and then cooled to room temperature. The off-white solid was filtered, washed with toluene (20 mL), diethyl ether (3 x 10 mL) and dried in vacuo. Yield 6.6 g (76 %). Crystals suitable for X-ray diffraction were grown by layering pentane over a saturated dichloromethane solution. [0085] 1H NMR (400 MHz, CDCI3): 5 11.35 (s, 1H, NH(imine)), 7.56 (t, 2H, J = 7.8 Hz, p-CH(2,6-diisopropylphenyl)), 7.30 (d, 4H, J = 7.8 Hz, m-CH(2,6-diisopropylphenyl)), 6.95 (s, 2H, -NCHCHN-), 6.87 (t, 1H, J = 7.5 Hz, p-CH(2,6-dimethylphenyl)), 6.73 (d, 2H, J = 7.4 Hz, m-CH(2, 6-dimethylphenyl)), 2.47 (sept, 4H, J = 6.8 Hz, CH(2, 6-diisopropylphenyl)), 2.25 (s, 3H, CH3(lmine)), 1.53 (s, 6H, o-CH3(xylyl)), 1.12 (d, 12H, J = 6.8 Hz, CH3(2,6- diisopropylphenyl)), 1.06 (d, 12H, J = 6.8 Hz, CH3(2,6-diisopropylphenyl)) [0086] 13CfH} NMR (100.6 MHz, CDCI3): 5 162.1 (s, -NC(imine)N-), 149.7 (s, - NC(imidazolin)N-), 145.7 (s, o-C(2, 6-diisopropylphenyl)), 135.3 (s, o-C(2, 6-xylyl)), 134.7 (s, C(2,6-xylyl)), 131.5 (s, p-CH(2,6-diisopropylphenyl)), 129.9 (s, C(2,6-diisopropylphenyl)), 127.5 (s, m-CH(2, 6-xylyl)), 126.9 (s, p-CH(2, 6-xylyl)), 124.9 (s, m-p-CH(2, 6- diisopropylphenyl)), 119.4 (s, -NCHCHN-), 28.9 (s, CH(2,6-diisopropylphenyl)), 25.5 (s, CH3(2,6-diisopropylphenyl)), 22.2 (s, CH3(2,6-diisopropylphenyl)), 20.6 (s, CH3(imine)), 17.7 (s, o-CH3(2, 6-xylyl) ) [0087] Anal. Calcd. For C37H48CIN4 (%): C, 76.19; H, 8.12; N, 9.61 ; Found (%): C, 68.56; H, 8.04; N, 8.54. Satisfactory combustion analysis was never obtained. Multiple analyses always gave lower C and N contents. [0088] HRMS (ESI+, CH3CN): Calculated for C37H48CIN4, m/z = 548.3879 [M-CI]+; Found: 548.3870 [M-CI]+ [0089] FTIR (Thin film): vC=N 1613 cm-1 , vC=C 1518 cm-1 [0090] Example 1.3: N-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-di-tert- butylimidazol-2-imine hydrochloride, I'BuN' mine-HCI (Compound I -3a)
Figure imgf000066_0001
[0091] A solution of 1 ,3-di-fe/f-butylimidazol-2-imine (685 mg, 3.51 mmol) in toluene (20 mL) was slowly added to a solution of /V-(2,6-dimethylphenyl)acetimidoyl chloride (618 mg, 3.41 mmol) in toluene (20 mL) at room temperature. The reaction mixture was heated to reflux at 125 °C for 12 h and then cooled to room temperature. The off-white solid was filtered, washed with toluene (10 mL), diethyl ether (2 x 10 mL) and dried in vacuo. Yield 890 mg (70 %). Crystals suitable for X-ray diffraction were grown by layering pentane over a saturated dichloromethane solution. [0092] 1H NMR (300 MHz, 296 K, CD2Ci : Major isomer (84 %): δ 1 1 .56 (s, 1 H, NH(im ine)) , 7.09-6.97 (m, 1 H, p-CH(2,6-xyiyi) + 2H, p-CH(2,6-xyiyi)) , 6.94 (s, 2H, -NCHCHN-), 2.33 (s, 6H,
Figure imgf000066_0002
2.24 (s, 3H, CH3{Wme)), 1 .45 (s, 18H, CH3{t -butyi)) I Minor isomer (16 %): 6 7.14 (br s, 2H, p-CH(2,6_xyiyi)) , 7.09-7.05 (m, 1 H, m-CH(2,6_xyiyi)) , 6.71 (s, 2H, -NCHCHN-), 2.27 (s, 3H, CH3{imme)), 1 .61 (s, 18H, CH3{t. i)), 1 .58 (s, 6H,
Figure imgf000066_0003
[0093] 13C{1H) NMR (75.5 MHz, 296 K, CD2CI2): Major isomer: δ 164.8 (s, - NC(im ine)N-), 148.7 (s, -NCf,m,dazo/m;N-), 136.3 (s, o-C(2,6-xyiyi)) , 135.8 (s, C(2,6-xylyl)) , 128.4 (s, m- CH(2 6.xylyl)), 127.7 (s, p-CH(2 6.xylyl)), 1 14.7 (s, -NCHCHN-), 60.4 (s, C(,Bu)), 29.1 (s, CH3(i_Bu)) , 22.2 (s, CH3(im ine)) , 19.3 (s, o-CH3(2,6-xyiyi)) . Minor isomer: δ 144.4 (s, -NC(imidaz0|in)N-), 128.4 (s, p-CH(2 6_xylyl)), 1 12.4 (s, -NCHCHN-), 59.0 (s, C{t.Bu)), 29.5 (s, o-CH3(2,6-xylyl)) . 28.7 (s, CH3(f_Bu)) , 19.5 (S, CH3(imine)). [0094] Example 1.4: N-(1 -(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine; IMesNAlmine (Compound 1-1 b)
Figure imgf000067_0001
[0095] To a suspension of IMesNAlmine-HCI l-1a (4.30 g, 8.6 mmol) in THF (40 mL) at -78 °C was added a cold THF (25 mL) solution of sodium fe/f-butoxide (868 mg, 9.03 mmol). The reaction mixture was stirred for 30 min at this temperature, and then slowly warmed to room temperature and stirred for an additional 4 h. During this time, the colour of the reaction mixture changed to pale yellow. The mixture was subsequently filtered through a plug of Celite™. Volatiles were removed at reduced pressure and the resulting solid was extracted with toluene (30 mL). The desired product was recovered by removing the solvent in vacuo. Yield: 2.94 g (74 %). [0096] 1H NMR (400 MHz, CD2Cl^: Major isomer (49 %): δ 6.89 (s, 4H, m- CH(mesityi)) , 6.73-6.69 (br m, 2H, m-CH(2,6-xyiyi)) , 6.54 (t, 1 H, 3J = 7.4 Hz, p-CH(2,6-xyiyi)) , 6.46 (s, 2H, -NCHCHN-), 2.26 (s, 6H, p-CH3{mesm), 2.17 (s, 12H, o-CH3{mesm), 1 .42 (s, 6H, o-CH3(2 6. xyiyi)) , 1 .22 (s, 3H, CH3{Wme)); Minor isomer A (38 %): δ 6.91 (s, 4H, m-CH{mesm), 6.73-6.69 (br m, 2H, m-CH(2,6-xyiyi)) , 6.60-6.57 (br m, 1 H, m-CH(2,6-xyiyi)) , 6.41 (s, 2H, -NCHCHN-), 2.30 (s, 6H, p-CH3{mesm), 1 .91 (s, 12H,
Figure imgf000067_0002
1 -50 (s, 3H,
CH3{Wme)); Minor isomer B (13 %): δ 6.93 (s, 4H, m-CH{mesm), 6.73-6.69 (br m, 2H, m-C/-/(2,6- xyiy,)) , 6.60-6.57 (br m, 1 H, m-CH(2,6-xyiyi)) , 6.17 (s, 2H, -NCHCHN-), 2.26 (s, 6H, p-CH3{mesm), 2.13 (s, 12H,
Figure imgf000067_0003
1 .53 (s, 3H, CH3{imme)). [0097] 1H NMR (600 MHz, C6D6): Major isomer (71 %): δ 7.03 (d, 2H, 3 J = 7.4 Hz, m-CH(2 6.xylyl)), 7.03 (t, 1 H, 3J = 7.4 Hz, p-CH(2 6.xylyl)), 6.69 (s, 4H, m-CH(mesityl)), 5.81 (s, 2H, -NCHCHN-), 2.25 (s, 12H, o-CH3{mesm), 2.08 (s, 6H, p-CH3{mesm), 1 .77 (s, 6H, o-CH3{2 6. xyiy,,) , 1 .54 (s, 3H, CH3{Wme)). Minor isomer A (23 %): δ 7.03 (d, 2H, 3J = 7.3 Hz, m-CH(2,6-xyiyi)) , 7.03 (t, 1 H, 3J = 7.3 Hz, p-CH(2,6.xyiyi)), 6.76 (s, 4H, m-CH{mesm), 5.64 (s, 2H, -NCHCHN-), 2.12 (s, 6H, p-CH3{mesm), 2.03 (s, 6H, o-CH3(2,6-xyiyi)) , 1 .91 (s, 12H, o-CH3(mesityi)) , 1 .80 (s, 3H, CH3(imine)) ; Minor isomer B (6 %) : δ 7.12 (t, 2H, 3J = 7.6 Hz, m-CH(2,6-xyiyi)) , (d, 1 H, 3J = 7.6 Hz, p-CH(2 6.xylyl)) , 6.76 (s, 4H, m-CH{mesm), 5.70 (s, 2H, -NCHCHN-), 2.25 (s, 6H, p-CH3{mesm), 2.1 1 (S, 12H,
Figure imgf000067_0004
-9 (S. 3H . CH3(im ine)) , 1 -77 (S, 6H, 0-CH3(2,6-xylyl)) . [0098] 13, CfH} NMR (158.8 MHz, C6D6): Major isomer: δ 158.9 (s, - NC(im ine)N-), 150.6 (S, C(2,6-xylyl)) , 148.7 (S, -NCf,m,dazo/m;N-), 138.1 (S, p-CH(2,6-xylyl)) , 136.2 (S, C(mesityi)) , 134.6 (s, o-C(mesityi)) , 129.4 (s, m-CH(mesityi)) , 128.8 (s, o-C(2,6-xyiyi)) , 120.6 (s, m- QmesityD &
Figure imgf000068_0001
1 15.6 (s, -NCHCHN-), 20.9 (s, p-CH3(mesityi) & CH3(i mine)) , 18.2 (s, o- CH3(mesityi) & o-CH3(2,6-xyiyi)) ; Minor isomor A: δ 152.9 (s, -N C(im ine)N-) , 151.6 (s, C(2,6-xyiyi)) , 143.1 (s, -NCfm dazo/n;N-), 138.6 (s, p-CH(2,6-xyiyi)) , 136.2 (s, C(meSityi)) , 133.2 (s, o-C(meSityi)) , 129.5 (s, m-CH(mesityi)) , 127.1 (s, o-C(2,6-xyiyi)) , 120.8 (s, m-CH(2,6-xyiyi) & p-CH(2,6-xyiyi)) , 1 14.7 (s, - NCHCHN-), 23.9 (s, CH3(im ine)) , 21.0 (s, p-CH3(mesityi)) , 18.8 (s, 0-CH3(2,6-xyiyi)) , 18.1 (s, 0- CH3(mesityi)) ; Minor isomor B: δ 151.9 (s, -NCf,m,dazo/m;N-), 143.1 (s, C(mesityi)) , 151.9 (s, C(2,6- xylyl)) , 129.5 (S, m-CH(mesityl)) , 128.3 (S, 0- C(mesityl)) , 127.8 (S, p-CH(mesityl)) , 120.8 (S, A7J-CH(2,6-xylyl) & p-CH(2,6_xyiyi)) , 1 12.5 (br s, -NCHCHN-), 18.6 (s, p-CH3(mesityi)) , 18.2 (o-CH3(mesityi) & s, o- CH3(2i6_xy|y|)) , 18.1 (S, CH3(jmine)) . [0099] Anal. Calcd. For C31H36N4 (%): C, 74.45; H, 7.26; N, 11.20; Found (%): C, 72.81; H, 7.26; N, 10.98. [00100] HRMS (ESI CH3CN): Calculated for C31H36N4, m/z = 464.2948 [Mf; Found: 464.2940 [ΜΓ [00101] FTIR (Thin film): vc=N 1616 cm'1, vc=c 1520 cm'1 [00102] Example 1.5: N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,6- diisopropylphenyl)imidazol-2-imine; IPrNAlmine (Compound l-2b)
[00103] To a suspension of IPrNAlmine lHCI l-2a (6.1 1 g, 10.5 mmol) in THF (40 ml.) at -78 °C was added a cold THF (25 ml.) solution of sodium te/f-butoxide (1.06 g, 1 1.0 mmol). The reaction mixture was stirred for 30 min at this temperature, and then slowly warmed to room temperature and stirred for an additional 4 h. During this time, the colour of the reaction mixture changed to pale yellow. The mixture was subsequently filtered through a plug of Celite™. Volatiles were removed at reduced pressure and the resulting solid was extracted with a toluene/pentane (3:1) mixture (3 x 30 ml_). The desired product was recovered by removing the solvent in vacuo. Yield: 5.16 g (90 %). [00104] 1H NMR (400 MHz, Major isomer (92 %): δ 7.33 (t, 2H, J = 7.7 Hz, p- CH(2,6-diisopropylphenyl)) > 7.18 (d, 4H, J = 7.7 Hz, 77-CH(2,6-diisopropylphenyl)) > 6.69 (d, 2H, J = 7.4 Hz, iT7-C/-/(2,6-dimethylphenyl)) , 6.52 (t, 1 H, J = 7.4 Hz, p-C - (2,6-dimethylphenyl)) > 6-46 (S, 2H, -NCHCHN-) , 3.04 (sept, 4H, J = 6.9 Hz, CH(2,6-diisopropyiphenyi)) , 1 -32 (s, 6H, o-CH3(xylyl)), 1 .25 (s, 3H,
1 .17 (d, 12H, J = 7.0 HZ, C/-/3(2]6-diisopropylphenyl)) , 1 .14 (d, 12H, J = 7.0 Hz, CH3(2,6- diisopropylphenyl)) ; ΜίΠΟΓ ISOmer (8 %)\ 5 7.40 (t, 2H, J = 7.8 HZ, p-CH(2,6-diisopropylphenyl)) , 7.22 (d, 4H, J = 7.8 Hz, m-CH(2,6-diisopropyiphenyi)) , 6.59-6.55 (d+ br, 3H, m-CH(2,6-di methylphenyl) + p-CH(2,6- dimethylphenyl)) , 6.25 (S, 2H, -NCHCHN-), 2.69 (Sept, 4H, J = 6.9 HZ, CH(2,6-dNsopropylphenyl)) , 1 -35 (s, 6H, o-CH3(xylyl)), 1 .19 (s, 3H, CH3 me)), 1 .06 (d, 12H, J = 6.9 Hz, CHsc.e-diisopropyiphenyi)) , 1 .02
Figure imgf000069_0001
[00105] "C 'H NMR (100.6 MHz, CD2CI2): Major isomer: δ 157.5 (s, -NC(imine)N-), 150.8 (S, C(2,6-xylyl)) , 148.6 (S, -NC(imjdazolin)N-), 147.1 (S, 0-Cp,6-diisopropylphenyi;) , 135.1 (S, C(2,6- diisopropylphenyl;) , 129.6 (S, p-CHp,6-diisopropylphenyi;) , 128.9 (S, 0-C(2,6-xylyl)) , 127.1 (S, ATI-CH(2,6-xylyl)) , 124.3 (s, m-CHf2,6.diisopropylphenyi;) 120.3 (s, p-CH(2,6-xyiyi)) , 1 17.3 (s, -NCHCHN-), 28.9 (s, CH(2,6_ diisopropylphenyl)) , 24.7 (S,
Figure imgf000069_0002
20.9 (S, CH3(jmjne)) , 18.1 (s, o-CH3(2,6-xyiyi)) ; Minor isomer: δ 153.9 (s, -NC,imine)N-), 145.6 (s, -NC(imidaz0|in)N-), 131 .1 (S, p-CH(2i6-diisopropylphenyi;) > 127.3 (S, A71-CH(2 6-xylyl)) , 124.7 (S,
Figure imgf000069_0003
120.6 (S, p-CH(2|6.xylyl)), 1 13.9 (s, -NCHCHN-), 28.9 (s, CH(2,6-diisopropyiPhenyi)) , 25.5 (s, CH3(2,6- diisopropylphenyl)) , 23.7 (S, CH3(imjne ) , 22.4 (S, CH3(2,6-diisopropylphenyl)) > 17.3 (S, 0-CH3(2,6-xylyl)) [00106] Anal. Calcd. For C37H48CIN4 (%): C, 76.19; H, 8.12; N, 9.61; Found (%): C, 68.56; H, 8.04; N, 8.54. [00107] HRMS (ESI+, CH3CN): Calculated for C37H48N4, m/z = 548.3872 [M]+; Found: 548.3879 [M]+ [00108] FTIR (Thin film): vc=N 1610 cm" , vc=c 1519 cm"1 [00109] Example 1.6: N-(2-iodo-1 -(4-chlorophenyl)ethylidene)-2,4,6- trimethylaniline
Figure imgf000069_0004
[00110] A solution of N-(2-iodo-1-(4-chlorophenyl)ethylidene)-2,4,6-trimethylaniline (1.5 g, 4.9 mmol) in acetone (10 mL) was added drop wise to a solution of sodium iodide (808 mg, 5.39 mmol) in acetone (20 mL) at room temperature. The reaction mixture was vigorously stirred for 24 hours and then evaporated to dryness. The orange brown crude was then extracted with pentane (2 χ 30 mL) and dried in vacuo at 0 °C to yield the product as orange yellow solid. Yield: 1.6 g (81 %). The solid was stored at - 40 °C in the absence of light. [00111] 1H NMR (300 MHz, C6D6, 295 K): δ 7.70 (d, 2H, J = 9.6 Hz, o-CH(4-chiorophenyi)) , 7.05 (d, 2H, J = 9.6 Hz, m-CH(4-chiorophenyi)) , 6.82 (s, 2H, m-CH(meSityi)) , 3.44 (s, 2H, CH2), 2.19 (s, 3H, p-CH3(mesityi)) , 1 -95 (s, 3H, o-CH3(mesityi)) - [00112] 13C{1H} NMR (300 MHz, C6D6, 296 K): 161.8 (s, -C(imine)-), 145.6 (s, C(mesityi)> , 137.2 (S, p-C(mesityl)) , 134.4 (S, p-C(4_chiorophenyl)) , 132.9 (S, C(4_ch|0rophenyl)) , 129.4 (S, m-CH(4_ chiorophenyi)) , 129.3 (s, o-CH(4_ch|0rophenyi)) , 128.8 (s, m-CH(meSityi)) , 35.2 (s, CH2), 20.8 (s, p- CH3(mesityl)) , 18.0 (S, 0-CH3(mesityl)) - [00113] Example 1.7: W-(2-(mesitylimino)-2-(4-chlorophenyl)ethyl))-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine hydroiodide, IMesNCH2 Almine■ HI (Compound I -4a) It is believed that this compound can be made as follows:
Figure imgf000070_0001
[00114] A solution of 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine (50 mg, 157 μηιοΓ) in pentane (2 mL) is slowly added to a solution of /V-(1-(4-chlorophenyl)-2-iodoethylidene)- 2,4,6-trimethylaniline (61 mg, 152 μηιοΓ) in pentane (2 mL) at room temperature. The reaction mixture is stirred for 48 h. The off-white solid is filtered, washed with pentane (2 x 5 mL) and dried in vacuo. [00115] Example 1.8: N-(4-Methylphenyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol- 2-iminecarboxamide, IPrN-C(=0)(NH-p-tol) (Compound IV-1a)
Figure imgf000071_0001
[00116] To a toluene-solution of imidazolin-2-imine IPrNH (19.3 mg, 4.78 x 102 mmol) was added p-tolyl isocyanate (6.36 mg, 4.78 x 102 mmol) neat or as a toluene solution. The reaction was generally stirred overnight although NMR experiments revealed that conversion to product proceeds almost instantaneously and in quantitative yield. The solvent was evaporated in vacuo and the crystalline beige solid isolated without further purification. If excess p-tolyl isocyanate was present, it could be removed through a cold pentane wash. [00117] 1H NMR (400 MHz, CDCI3): δ 7.40 (t, J = 7.7 Hz, 2H, p-H DIPP), 7.24 (s, 2H, m-H DIPP), 6.78 (overlapping doublets, 4H, o-H + m-H p-tolyl), 6.60 (s, 2H, NCHCHN), 6.16 (br. s, 1 H, NH), 2.96 (sept, dt, J = 13.7, 6.8 Hz, 4H, methine-H IPr), 2.15 (s, 3H, CH3 p-tolyl), 1.30 (d, J = 6.8 Hz, 14H, IPr-CH3), 1.20 (d, J = 6.9 Hz, 13H, IPr-CH3) ppm. [00118] 13C NMR (101 MHz, CDCI3): δ 157.32, 150.49, 146.42, 138.08, 133.08, 129.92, 129.59, 128.68, 123.91 , 18.47, 1 16.62, 28.83, 24.61 , 23.31 , 20.60 ppm. [00119] Example 1.9: N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2- iminecarboxamide, IMesN-C(=0)(NH-p-tol) (Compound IV-2a)
Figure imgf000071_0002
[00120] IMesN-C(=0)(NH-p-tol) IV-2a was prepared in a manner analogous to that described for the synthesis of compound IV-1a except using imidazolin-2-imine IMesNH.
[00121] Ή NMR (300 MHz, 293 K, CeDe) δ 7.02 (d, J
tolyl), 6.73-6.70 (s, 6H, m-H mesityl + m-H p-tolyl), 6.36 (br. s, 1 H, NH), 5.83 (s, 2H, NCHCHN), 2.27 (s, 12H, 0-CH3 mesityl), 2.06 (s, 6H, p-CH3 mesityl), 1 .94 (s, 3H, CH3 p- tolyl) ppm. [00122] "C Λ/ R (707 MHz, 293 K, CeDe): δ 157.99 (C=0), 149.79 (NNC=N), 139.42 (ipso-C p-tolyl), 138.35 (p-C mesityl), 135.94 (ipso-C mesityl), 133.97 (o-C mesityl), 129.43 (m-CH mesityl), 129.39 (p-C p-tolyl) 128.99 (m-CH p-tolyl), 1 18.21 (o-CH p-tolyl), 1 15.41 (NCHCHN), 21 .01 (p-CH3 mesityl), 20.65 (CH3 p-tolyl), 18.25 (0-CH3 mesityl) ppm. [00123] IR (cm-1) 1642 (C=0). [00124] Example 1.10: N-(4-Methylphenyl)-N-trimethylsilyl-1 , 3- bis(mesityl)imidazol-2-iminecarboxamide, IMesN-C(=0)(N(SiMe3)-p-tol) (Compound IV-2b)
Figure imgf000072_0001
[00125] To a pentane solution of N-silylated imidazolin-2-imine IMesNSiMe3 (275 mg, 0.702 mmol) was added p-tolyl isocyanate (93.5 mg, 0.702 mmol) neat or as a solution. The reaction was stirred for 36 h at which time the precipitated product was collected by filtration and washed with cold pentane. Yield: 85%. NMR experiments carried out in C6D6 revealed that quantitative conversion to product proceeds in approximately 3 hours however, reactions conducted in pentane led to purer products. [00126] 1H NMR (300 MHz, 293 K, C6D6): δ 6.89 (d, J = 7.9 Hz, 2H, o-/m-H p- tolyl), 6.79 (d, J = 8.1 Hz, 2H, o-/m-H p-tolyl), 6.76 (s, 4H, m-CH mesityl), 5.73 (s, 2H, NCHCHN), 2.16 (s, 2H, p-CH3 mesityl), 2.12 (s, 3H, p-CH3 p-tolyl), 2.1 1 (s, 12H, 0-CH3 mesityl), 0.1 1 (s, 9H, SiMe3). [00127] Example 1.11 : Lithium N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2- iminecarboxamide, Li[(IMesN-C(=0)(N-p-tol)] (Compound V-1a)
Figure imgf000073_0001
[00128] To a THF-solution of IMesN(C=0)N(H)tolyl (IV-1a) (216 mg, 0.477 mmol) was added a solution of nBuLi in hexanes (2.5M, 200 uL, 0.500 mmol) dropwise. The pale yellow solution turned dark orange upon addition. The solution was stirred for 20-30 minutes at room temperature before using without further purification. In order to confirm that the Li salt (V-1a) was in fact prepared, the TMS adduct (IV-2b) was synthesized by quenching the Li- salt with trimethylsilyl chloride. To a C6D6 solution of IV-1a (15.4 mg, 3.40 x 10-2 mmol) in an NMR tube fitted with a rubber septum was added nBuLi neat (14.3 uL, 3.75 x 10-2 mmol) via microsyringe. The 1H NMR revealed a broad baseline with at least four signals in the vinylic region. Addition of neat TMSCI (4.76 uL, 3.75 x 10-2 mmol) via microsyringe, dramatically cleaned up the NMR spectrum with only 1 signal in the vinylic region. The overall spectrum was consistent with the TMS-adduct IV-2b prepared by reaction of the N-silylated imidazolin- 2-imide with p-tolyl isocyanate. [00129] Example 1.12: Pyridine-2-6-bis[1 ,3-bis(2,4,6-trimethylphenyl)imidazolin- 2-methanaminium)] ditosylate, [(IMesN-CH2)2Py](OTs)2 (Compound I -5a)
Figure imgf000073_0002
[00130] To a stirred toluene (50 mL) solution of pyridine-2,6-bismethylene ditosylate (3.6 g, 7.9 mmol) was slowly added a toluene ( 30 mL) solution of 2,4,6- trimethylphenylimidazol-2-imine at room temperature. The colour of the reaction mixture changed to bright red and the mixture was slowly heated to reflux at 125 °C for 48 h. Reaction mixture was cooled to room temperature and the precipitated solid was filtered, washed with toluene (30 mL) and diethylether (50 mL) to produce the light pink solid. Yield: 7.5 g, (87 %). Crystals suitable for X-ray diffraction studies were grown by layering pentane onto the saturated dichloromethane solution. [00131] 1H NMR (400 MHz, 295 K, CDCI3) : δ 8.94 (t, 2H, J = 6.2 Hz, Imine NH), 7.56 (d, 2H, J = 7.9 Hz, Tosyl p-CH), 7.34 (t, 1 H, J = 7.7 Hz, Pyridine p-CH), 7.07 (d, 2H, J = 7.8 Hz, Tosyl o-CH), 6.96 (d, 2H, J = 7.7 Hz, Pyridine m-CH) , 6.88 (s, 8H, Mesityl m-H) , 6.55 (s, 4H, -NCHCHN-) , 4.13 (d, 4H, J = 6.3 Hz, -NCH2C(aromatic)-) , 2.33 (s, 12H, Tosyl p-methyl CH3), 2.24 (s, 12H , Mesityl p-CH3), (s, 24H, Mesityl o-CH3) , [00132] 13C{1H) NMR (75.5 MHz, 295 K, CDCI3) : 17.4 (s, Mesityl o-CH3), 21 .1 (s, Mesityl p-CH3), 21 .2 (s, Tosyl p- ethyl CH3), 46.8 (s,-NCH2C(aromatic)-), 1 17.9 (s, -NCHCHN-), 1 19.7 (s, Pyridine m-CH), 126.1 (s, Tosyl o-CH), 126.1 (s, Tosyl o-CH) , 126.0 (s, Tosyl m- CH), 128.8 (s, -NCfmes(fy()), 129.8 (s, Mesityl m-CH) , 135.6 (s, o-Cfmes(M)), 136.9 (s, Pyridine p- CH), 138.3 (s, Tosyl -SCfaromaf,c;) , 141 .0 (s, Mesityl p-CH) , 144.0 (s, Tosyl p-methyl C(aromatic)) , 144.4 (s, Pyridine o-Cfaromaf,c;), 155.7 (s, -NCN-). [00133] HRMS (ESI CH3CN): Calculated for C49H56N7, m/z = 742.4592 [M-(OTs)2- H]+; Found: 742.4581 [M-(OTs)2-H]+ [00134] Example 1.13: Pyridine-2-6-bis[1 ,3-bis(2,6-diisopropylphenyl)imidazolin- 2-methanaminium)] ditosylate, [(IPrN-CH2)2Py](OTs)2 (Compound l-6a)
Figure imgf000074_0001
[00135] To a stirred toluene (50 mL) solution of pyridine-2,6-bismethylene ditosylate (1 .9 g, 4.3 mmol) was slowly added a toluene (30 mL) solution of 2,6- diisopropylphenylimidazol-2-imine (3.6 g, 9.1 mmol) at room temperature. The reaction mixture was slowly heated to reflux at 125 °C for 48 h and cooled to room temperature. The precipitated white solid was filtered, washed with toluene 10 mL and then with pentane (10 mL). The crude was dissolved in the minimum amount of dichloromethane (10 mL) and then added drop wise to a stirred diethyl ether (100 mL). The reaction mixture was stirred 10 min, filtered, washed with diethyl ether (20 mL) , pentane (20 mL) and dried in vacuo. Yield: 4.7 g (88 %) Crystals suitable for X-ray diffraction studies were grown by layering pentane onto the saturated dichloromethane solution. [00136] 1H NMR (300 MHz, 295 K, D20): δ 7.72-7.55 (m, 8H, CH(aromatic)), 7.52-7.22 (m, 17H, CH(aromatlc)), 6.96 (d, 2H, J = 6.2 Hz, Pyridine -CH), 3.82 (s, 4H, -NCH2C(aromatic)-) , 2.62 (spet, 8H, J = 6.0 Hz, C/-/(2,6-diisopropyiphenyi)) , 2.37 (s, 6H, Tosyl p-methyl CH3), 1 .28-1 .15 (m, 36 H, C/-/3(2 i6-diisopropylphenyl)) > 1 - 10 (d, 12H, J = 6.0 Hz, CH3(2i6-diisopropylphenyl)) [00137] HRMS (ESI+, CH3CN): Calculated for C61H8oN7, m/z = 910.6475 [M]+; Found: 910.6477 [M]+ [00138] Example 1.14: N-(2-oxo-2-phenylethyl))-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine hydrobromide, IMesNCH2 AKetone HBr (Compound X-1a)
Figure imgf000075_0001
[00139] To a toluene (5 mL) solution of 2-bromoacetophenone (476 mg, 2.39 mmol) was added a toluene (10 mL) solution of 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine IMesNH (763 mg, 2.39 mmol). The reaction mixture was stirred for 30 min at room temperature. During this time, colour of the reaction mixture changed to bright red with precipitation of an off-white solid. Reaction mixture was then heated to reflux for 2 h and then cooled to room temperature. The off-white solid was filtered, washed with toluene (10 mL), diethylether (10 mL), pentane (10 mL) and dried in vacuo. Yield: 1 .1 g (89 %). [00140] 1H NMR (400 MHz, CDCI3, 292 K), Major isomer (82 %): δ 7.99 (t, 1 H, J = 6.5 Hz, NH), 7.49 (t, 1 H, J = 7.4 Hz, p-CH{phenyl)), 7.46 (d, 1 H, J = 7.9 Hz, o-CH(phenyi)) , 7.30 (t, 1 H, J = 8.0 Hz, m-CH(phenyi)) , 6.89 (s, 4H, m-CH{mesm), 6.77 (s, 2H, -NCHCHN-), 4.48 (d, 2H, J = 7.2 Hz, N-C/-/2), 2.23 (s, 12H, o-CH3(mesityi)) , 2.21 (s, 6H, p-CH3{mesm); Minor isomer (18 %): δ 7.06 (s, 4H, m-CH{mesm), 6.83 (s, 2H, m-CH{phenyl)), 6.69 (s, 2H, -NCHCHN-), 2.35 (s, 6H, m-C/-/3(meSityi)) , 2.16 (s, 6H, o-C/-/3(meSityi)) - [00141] 13C{1H} NMR (100.6 MHz, CDCI3, 294 K): Major isomer: δ 1 92.2 (s, C(ketone)) , 144.8 (s, -NC(imidazolin)N-), 141 .4 (s, Cfmesityi;), 1 36.0 (s, o-C(mesm), 1 33.7 (s, p-C(phenyi)), 1 30.0 (s, -Cfmesityy), 128.4 (s, o-C(phenyi)), 127.5 (s, m-Qpheny ) , 1 1 7.7 (s, -NCHCHN-), 48.6 (s, C(CH2)), 21 .1 (s, p-CH3(mesityi)), 1 7.8 (s, p-CH3(mesityi)) ; Minor isomer: δ 145.2 (s, -NC(IMIDAZ0|IN)N-) , 141 .4 (S, O-Cfmesityy), 35.6 (S, Cfmesityy), 1 30.4 (S, -Cfmesityy), 1 1 7.2 (S, -NCHCHN-), 21 .2 (S, p-CH3(mesityl)), 1 7.6 (S, p-CH3(mesityl)) - [00142] Example 1.15: N-(2-oxo-2-phenylethyl))-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine, I MesNCH2 A Ketone (Compound X-1 b)
Figure imgf000076_0001
[00143] A toluene (20 mL) solution of 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine IMesNH (2.0 g, 6.3 mmol) was added dropwise to a toluene (30 mL) solution of 2- bromoacetophenone (1 .3 g, 6.3 mmol) at room temperature. The reaction mixture was stirred for 30 min at room temperature. During which time, the colour of the reaction mixture changed to bright red with precipitation of an off-white solid. Reaction mixture was then heated to reflux for 2 h. Precipitated solid was filtered, washed with toluene (1 0 mL), diethylether (2 χ 1 0 mL) and finally with pentane (1 0 mL). Yield: 2.6 g (80%). The crude (2.6 g, 5.0 mmol) was suspended in THF (30 mL) and a solution of NaHMDS (938 mg, 5.1 1 mmol) in THF (1 0 mL) was added dropwise at -78 °C. Reaction mixture was stirred for 1 0 min at this temperature, slowly warmed to room temperature and stirred for 30 min. The pale yellow solution was filtered, evaporated to dryness and extracted with pentane (2 χ 30 mL). The off-white solid was dried in vacuo and the pale yellow solution was concentrated to 1 5 mL and left at -78 °C for four hours to precipitate product. The precipitated off-white solid was washed with cold (-78 °C) pentane (1 0 mL) and dried in vacuo. Yield: 1 .8 g (82 %). [00144] Example 1.16: Sodium 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N- (2-phenylethenolate), Na[IMesNAethenolate] (Compound Xl-1a)
Figure imgf000077_0001
\ [00145] To a THF (2 mL) suspension of NaH (1 1.5 mg, 480 μηιοΙ) at -40 °C was slowly added a cold (-40 °C) solution of /V-(2-oxo-2-phenylethyl))-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine (150 mg, 343 μηιοΓ) in THF (5 mL). The reaction mixture was slowly warmed to room temperature and stirred for 60 min. During which time, the colour of the reaction mixture slowly changed to intense yellow. It was filtered and evaporated to dryness to yield yellow solid. Pentane (5 mL) was added to precipitate the product, which was filtered, washed with pentane (2 x 5 mL) and dried in vacuo. Yield: 137 g (87%). [00146] 1H NMR (300 MHz, C6D6, 295 K): δ 7.26 (t, 2H, 3 J = Hz, m-CH{phenyl)), 7.09 (t, 1 H, 3J = Hz, p-CH(phenyi)) , 6.99 (s, 1 H, m-CH{mesm), 6.83 (d, 2H, 3J = Hz, o-CH(phenyi)) , 6.75 (s, 1 H, m-CH(mesityi)) , 6.30 (s, 1 H, m-CH{mesm), 6.21 (s, 1 H, -NCH), 6.09 (s, 1 H, m-CH{mesm), 5.61 (d, 1 H, 3J = Hz -NCHCHN-), 5.57 (d, 1 H, 3J = Hz -NCHCHN-), 2.49 (s, 3H, CH3{mesm) , 2.28 (s, 3H,
Figure imgf000077_0002
2.05 (s, 3H, C - 3(meSityi)) , 1 -89 (s, 3H, C/-/3(mesityl))■ [00147] 13C{1H) NMR (100.6 MHz, C6D6, 297 K): δ 150.3 (s, CH=C(0)Phenyl), 146.5 (s, Cfmesityij) , 141.5 (s, -NC(imidaz0|in)N-), 137.9, 137.7, 137.4, 136.9, 135.8, 135.5,135.2, 133.3 (s, Cfmesityi;), 130.3, 129.6, 129.0, 128.7 (s, m-CHfmesityi;), 127.7 (s, m-CH(phenyl)), 124.5 (s, o- CH(phenyi)) , 122.5 (s, p-CH(phenyi)) , 1 14.3 (s, -NCHCHN-), 1 13.8 (s, -NCHCHN-), 103.8(s, CH=C(0)), 2.5, 2.3, 2.2, 2.1 , 2.0, 1.9 (s, ΟΗ3Μο). Example 2: Synthesis of the Transition Metal Complexes
[00148] Example 2.1 : N-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine teterachlorotitanium(IV); Ti(IMesNAlmine)CI4 (4a)
Figure imgf000078_0001
[00149] To a suspension of IMesNAlmine HCI l-1a (300 mg, 0.60 0.599 mmol) in benzene (5 mL) was added sodium fe/f-butoxide (56.5 mg, 0.588 mmol) as a solid in one portion. Reaction mixture was stirred for 2 h at room temperature and then filtered through a plug of Celite™. The solid was washed with benzene (1 mL) and the combined organic fractions were dried in vacuo for 1 h at room temperature. The off-white solid was redissolved in benzene (5 mL) and added dropwise to a stirred solution of TiCI4(THF)2 (192.3 mg, 0.576 mmol) in benzene (2 mL) at room temperature. The color of the reaction mixture changed to bright red from the original yellow solution. The reaction mixture was stirred for 45 min and the precipitated brick red solid was filtered, washed with benzene (2 x 3 mL), pentane (5 mL) and dried in vacuo. Yield: 263 mg (70%). Single crystals suitable for X-ray diffraction study were grown from a saturated CH3CI solution at room temperature. [00150] 1H NMR (300 MHz, CDCI3): δ 7.12 (s, 4H, m-CH{mesm), 7.02 (s, 2H, - NCHCHN-), (br s, 3H, m-CH(2,6_xylyl) & p-CH(2,6_xylyl)), 2.44 (s, 6H, p-CH3{mesm), 2.38 (br s, 12H, 0-C - 3(mesityl)) , 2.14 (S, 6H, 0-C/-/3(2,6-xylyl)) , 1 -69 (S, 3H, CH3(lmme)) , [00151] 13C{1H) NMR (100.6 MHz, CD2Cl^: δ 175.0 (s, -NC(imine)N-), 147.0 (s, - NC(imidaz0|in)N-), 144.6 (s, C(2,6-xyiyi)) , 141 .5 (s, p-C{mesm), 133.8 (br s, C{mesm), 133.8 (s, o-C(2 6- xylyl)), 131 .2 (s, o-C(mesityl)), 130.4 (br s, m-CH(mesityl)), 129.1 (s, m-CH(2 6.xylyl)), 127.3 (s, p-CH(2 6. xylyl)), 122.2 (s, -NCHCHN-),21 .4 (s, p-CH3(mesityi)) , 20.3 (s, o-CH3(2,6-xylyl)) , 20.0 (s, CH3(im ine)) , 19.6 (br s, o-CH3(mesityi)) . [00152] Anal. Calcd. For C31H36Cl4N4Ti (%): Satisfactory combustion analysis was never obtained due to the sensitive nature of the complex. [00153] MS (ESI CH2Cl^ Calculated for C31H36CI4N4Ti, m/z = 464.29 [M-TiCI4]+; Found: 464.30 [M-TiCI4]+ [00154] Example 2.2: N-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,6- diisopropylphenyl)imidazol-2-imine teterachlorotitanium(IV); Ti(IPrNAlmine)CI4 (4b)
Figure imgf000079_0001
[00155] To a suspension of IPrNAlmine HCI l-2a (165 mg, 0.283 mmol) in benzene (5 mL) was added sodium fe/f-butoxide (26.7 mg, 0.277 mmol) as a solid in one portion.
Reaction mixture was stirred for 2 h at room temperature and then filtered through a plug of Celite™. The solid was washed with benzene (1 mL) and the combined organic fractions were dried in vacuo for 30 min. The off-white solid was redissolved in benzene (3 mL) and added dropwise to a stirred solution of TiCI4(THF)2 (86.9 mg, 0.260 mmol) in benzene (2 mL) at room temperature. The color of the reaction mixture changed to bright red from the original yellow solution. The reaction mixture was stirred for 45 min and the precipitated brick red solid was filtered, washed with benzene (2 x 3 mL), pentane (10 mL) and dried in vacuo. Yield: 152 mg (76 %). [00156] 1H NMR (400 MHz, CDCI3): δ 7.55 (t, 2H, 3 J = 7.8 Hz, p-CH(2,6.diis0propylphenyi)) , 7.39 (d, 4H, 3 J = 7.8 Hz, m-CH(2,6-diisopropyiphenyi)), 7.30 (s, 2H, -NCHCHN-), 7.00-6.88 (m, 3H, -CH(2 6-xy|y|) & m-CH(2 6-xy|y|)), 2.95 (br S, 4H, H, 0-CH3(2 6xy|y|)), 1 .64 (s, 3H, CH3(imine)) , 1 .46 (br d, 12 H, 3J =
Figure imgf000079_0002
1 .16 (d, 12H, 3J = 6.7 HZ, CH3(2,6-diisopropylphenyl)) [00157] 13C{1H) NMR (100.6 MHz, CD2Cl^: δ 173.9 (s, -NC(imine)N-), 148.7 (s, - NC(jmjdazolin)N-) , 146.4 (S, O-Cp, 6-diisopropylphenylj) > 144.5 (S, C(2,6-xylyl)), 133.9 (S, 0-C(2,6-xylyl)) , 132.1 (S, p-CH(2i6-diisopropylphenyi ) > 131 .9 (S, Cp,6-diisopropylphenylj), 129.2 (S, A77-CH(2,6-xylyl)), 127.1 (S, p- CH(2,6-xylyl)) , 125.2 (S, m-CHf2,6-diisopropylphenyi;) , 123.4 (S, -NCHCHN-), 29.8 (S, CH(2,6- diisopropylphenyl)) , 26.6 (S,
Figure imgf000079_0003
20.7 (S, 0-CH3(2i6- xylyl)), 17.9 (S, CH3(jmjne)) . [00158] MS (ESI+, CH2Cl^ Calculated for C37H48CI4N4T1, m/z = 548.39 [M-TiCI4]+; Found: 548.40 [M-TiCI4]+ [00159] Example 2.3: N-(1 -ethylimino-2,6-dimethylphenyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-iminedichloropalladium(ll) dimer; [Pd(IMesNAlmine)CI2]2 (5a)
Figure imgf000080_0001
Mes 2,6-xylyl J [00160] To a suspension of IMesNTImine.HCI l-1a (200 mg, 0.399 mmol) in benzene (5 mL) was added sodium fe/f-butoxide (37.7 mg, 0.392 mmol) as a solid in one portion and the reaction mixture was stirred for 2 h at room temperature. The reaction mixture was then passed through a plug of Celite™ and the solid was washed with benzene (1 mL). The combined fractions were added dropwise to a stirred solution of Pd(CH3CN)2 Cl2 (101 .6 mg, 0.392 mmol) in benzene (1 mL) at room temperature. The color of the reaction mixture changed from the original yellow solution to orange brown. The reaction mixture was further stirred for 2 h and the precipitated solid was filtered, washed with benzene (2 x 3 mL). Solid was dissolved in minimum amount of dichloromethane and the solution was passed through a plug of neutral alumina. The plug was washed with dichloromethane (1 mL) and the orange brown solution was added dropwise to stirred diethyl ether (10 mL). The product was isolated as yellow brown solid, which was dried dried under high vacuum for 12 h. Yield: 190 mg (76 %). [00161] 1H NMR (400 MHz, CDCI3): δ 6.87 (s, 4H, m-CH{mesm), 6.80 (t, 1 H, 3 J = 7.2 Hz, p-CH(2,6-xyiyi)) , 6.70 (d, 2H, 3J = 7.4 Hz, m-CH{2fi_xyW), 6.56 (s, 2H, -NCHCHN-), 2.39 (s, 3H, CH3(im ine)) , 2.30 (S, 6H, 0-CH3(2,6-xylyl)) , 1 -82 (S, 12H,
Figure imgf000080_0002
76 (s> 6H> P- CH3(mesityl)) , [00162] 13C{1H) NMR (100.6 MHz, CDCI3): δ 162.3 (s, -NC(imine)N-), 146.4 (s, p- C(mesityi)) , 144.6 (s, -NCf,m,dazo/m;N-), 140.3 (s, o-C{2,6.xm), 134.9 (s, o-C{mesm), 130.8 (s, C(mesityl)) , 130.1 (S, C(2,6-xylyl)) , 129.7 (S, m-CH(mesityl)) , 127.4 (S, m-CH(2,6-xylyl)) , 124.3 (S, P-CH(2,6- xylyl)), 1 16.3 (s, -NCHCHN-), 26.3 (s, CH3(imine)) , 21 .2 (s, o-CH3(2,6-xyiyi)) , 20.2 (s, p-C 3{mesm), 17.7 (S, 0-CH3(mesityl)) - [00163] Anal. Calcd. For C31H36CI2N4Pd. CH2CI2 (%): C, 52.87; H, 5.27; N, 7.71 ; Found (%): C, 51 .8; H, 5.30; N, 7.79. Repeated attempts always gave lower C contents. [00164] HRMS (ESI+, CH3CN): Calculated for Ce^CUNePdz, m/z = 1245.3009 [M- Cl]+; Found: 1245.2864 [M-CI]+ [00165] FTIR (Thin film): vc=N 1595 cm 1 , vc=c 1519 cm 1 [00166] Example 2.4: N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,6- diisopropylphenyl)imidazol-2-imine dichloropalladium(ll) dimer; [Pd(IPrNAlmine)CI2]2 (5b)
N N N
D I PP 2,6-xylyl 2
[00167] To a suspension of IPrNTImine HCI (215 mg, 0.368 mmol) in benzene (4 mL) was added sodium fe/f-butoxide (36.1 mg, 0.376 mmol) as solid in one portion and the reaction mixture was stirred for 2 h at room temperature. The reaction mixture was then passed through a plug of Celite™ and the solid was washed with benzene (1 mL). The combined organic fractions were added dropwise to a stirred solution of Pd(CH3CN)2CI2 (93.4 mg, 0.357 mmol) in benzene (2 mL) at room temperature. The color of the reaction mixture changed from the original yellow solution to orange brown and the reaction mixture was stirred for 2 h. The precipitated solid was filtered, washed with benzene (2 x 3 mL), pentane (3 mL) and dried in vacuo. Yield: 198 mg (76 %). Single crystals suitable for X-ray diffraction study were grown by layering pentane onto a saturated CH2CI2 solution. [00168] 1H NMR (400 MHz, CDCI3,): δ 7.45 (t, 2H, 3 J = 7.7 Hz, p-CH(2,6_diisopr0pylphenyi)) , 7.23 (d, 4H, 3 J = 7.8 Hz, m-CH(2,6_diiSopropyiphenyi)), 6.76 (m, 2H, -NCHCHN- & 1 H, p-CH(2 6.xylyl)), 6.62 (d, 2H, 3 J = 7.4 Hz, m-CH{2fi_xy¥)), 2.59 (s, 3H, CH3(imine)) 2.48 (m, 4H, CH(2 6.
diisopropylphenyl)) , 1 -47 (S, 6H, 0-C " 3(2,6xylyl)) , 1 -03 (d, 12 H, 3J = 6.5 Hz, CH3(2,6-diisopropylphenyl))> 1 -01 (d, 12H, 3J = 6.5 HZ, C - 3(2,6-diisopropylphenyl)) [00169] 13C{1H) NMR (100.6 MHz, CDCI3): δ 162.7 (s, -NC(imine)N-), 150.1 (s, - NC(jmjdazolin)N-) , 146.7 (S,
Figure imgf000081_0001
146.4 (S, C(2,6-xylyl)), 135.5 (S, 0-C(2,6-xylyl)), 131.6 (S, C(2i6-diisopropylphenyi )> 131.3 (S, p-CH(2i6-diisopropylphenyi ) > 128.2 (S, A77-CH(2,6-xylyl)) , 125.1 (S, ATJ-p- CHp e-diisopropyiphenyi;) , 124.8 (s, p-CH(2 6_xylyl)), 1 19.0 (s, -NCHCHN-), 29.3 (s, CH(2 6_
diisopropylphenyl)) , 27.9 (S, CH3(jmjne)), 25.8 (S, CH3(2i6_diisopropylphenyl))■ 22.7 (S, CH3(2i6_diisopropylphenyl))■ 20.5 (S, 0-CH3(2,6-xylyl)) [00170] Anal. Calcd. For C37H48CI2N4Pd (%): C, 61.20; H, 6.66; N, 7.72; Found (%): C, 60.92; H, 6.51 ; N, 7.84. [00171] HRMS (ESI CH3CN): Calculated for C37H48CI2N4Pd, m/z = 653.2829 [M- Cl2]+; Found: 653.2779 [M-CI2]+ [00172] FTIR (Thin film): vc=N 1599 cm 1 , vc=c 1518 cm 1 [00173] Example 2.5: (N-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine)-ter1-butylimidodichlorotitanium(IV);
Figure imgf000082_0001
,Mes
Mes Ti=N¾u
CI CI [00174] To a solution of Ti(N'Bu)CI20"MEDA) (61 .1 mg, 0.199 mmol) in benzene (2 mL) was added dropwise a benzene (5 mL) solution of IMesNAlmine 1-1 b (102 mg, 0.219 mmol) at room temperature. The reaction mixture changed to a bright orange-red colour from the original lemon yellow. The reaction mixture was stirred for 12 h at this temperature and was subsequently filtered through a plug of Celite™. Volatiles were removed at reduced pressure and the crude was redissolved in minimum amount of methylene chloride and layered with pentane. Yellow needles formed overnight and were collected, washed with pentane and dried in vacuo. Yield: 107 mg (82 %). Single crystals suitable for X-ray diffraction study were grown by layering a saturated methylene chloride with pentane at room temperature. [00175] 1H NMR (400 MHz, CDCI3): δ 6.94 (br s, 4H, m-CH{mesm), 6.94-6.91 (br m, 3H, m-CH(2,6_xylyl) & p-CH(2 6.xylyl)), 6.88 (s, 2H, -NCHCHN-), 2.32 (s, 6H, p-CH3{mesm), 2.26 (br s, 12H,
Figure imgf000082_0002
1 .26 (s, 3H, CH3{imme)), 0.63 (s, 9H, tert- butyl-CH3) [00176] 13CfH} NMR (100.6 MHz, CD2Cl^: δ 168.3 (s, -NC(imine)N-), 146.8 (s, C(2,6- xylyl)), 144.9 (s, -NC(imidazolin)N-), 140.2 (s, p-C{mesm), 134.1 (br s, C{mesm), 131 .6 (s, o- C(mesityi)), 131 .1 (s, o-C(2,6-xyiyi)), 130.4 (br s, m-CH(me8ityi)) , 128.1 (s, m-CH(2,6-xyiyi)), 125.1 (s, p- CH(2,6_xylyl)) , 1 19.1 (s, -NCHCHN-) , 71 .5 (s, C(tert_butyl)) , 30.4 (s, CH3(tef/-butyi)) , 21 .1 (s, p- CH3(mesityi)) , 19.3 (br s, o-CH3(mesityi)), 18.6 (s, o-CH3(2 6_xyiyi)), 18.1 (s, CH3(imine)) , [00177] MS (ESI+, CH2Cl^ Calculated for C31 H36CI4N4T1, m/z = 464.29 [M-TiCI4]+; Found: 464.30 [M-TiCI4]+ [00178] Example 2.6: (N-(1 -(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-imine)-(2-tert-butylphenylimido)dichlorotitanium(IV);
Figure imgf000082_0003
Mes
+2L 2 ,6-Xylyl
Mes 1 Ti=N-2-fBuPh
/ V
CI CI [00179] To a solution of Ti(N-2-'BuPh)CI20"MEDA) (191 mg, 0.502 mmol) in benzene (10 mL) was added dropwise a benzene (10 mL) solution of IMesNAlmine 1-1 b (245 mg, 0.527 mmol) at room temperature. The colour of the reaction mixture turned from brown to bright orange-yellow. The reaction mixture was stirred for 12 h at this temperature. The precipitated off-white was filtered and washed with benzene (5 mL), pentane (5 mL) and dried under reduced pressure. The crude was redissolved in methylene chloride (2 mL) and layered with pentane. The resulting pale orangish off-white solid was collected, washed with pentane and dried in vacuo. Yield: 285 mg (78 %). [00180] 1H NMR (400 MHz, CD2Cl^: δ 6.94 (br s, 4H, m-CH{mesm), 6.93 (s, 2H, - NCHCHN-), 6.83 (br s, 3H, m-CH{Z6.xm & p-CH(2,6-xyiyi)) , 6.81 (d, 1 H, J = 7.8 Hz, o-CH(2A. euPh)) , 6.61 (t, 1 H, J = 7.4 Hz, m-CHp+suPh)) , 6.49 (t, 1 H, J = 7.4 Hz,
Figure imgf000083_0001
5.93 (d, 1 H, J = 7.7 Hz, m-CH(2-f-BuPh)) , 2.25 (br s, 18H, o-C/-/3(meSityi) + p-C/-/3(meSityi)) , 1 .78 (s, 6H, o- CH3(2,6-xyiyi)) , 1 -33 (s, 3H, CH3(im ine)) , 1 .22 (s, 9H, terf-butyl-CH3) [00181] 13C{1H) NMR (100.6 MHz, CD2Cl^: δ 170.4 (s, -NC(imine)N-), 161 .2 (s, C(2.t. euPh)) , 146.9 (s, -NC(imidaz0|in)N-), 143.6 (s, C(2,6-xyiyi)) , 140.8 (s, 0-C{mesm), 140.5 (s, o-C2{2-t- BuPh)) , 132.2 (S, 0-C(2 6-xylyl)) , 131 .6 (S, m-C3(2-f-BuPh)) , 130.8 (S, p-C(mesityl)) , 130. 8 (m-CH(mesityl)) , 130.2 (br s, C(mesityl)), 128.4 (s, m-CH(2,6-xyiyi)) , 125.6 (s, p-CH(2,6-xylyl)) , 125.2 (s, m-Cgp+BuPh)) , 124.7 (s, 0-C6(2-f-BuPh>) , 124.7 (s,
Figure imgf000083_0002
120.3 (s, -NCHCHN-), 35.3 (s, C(tert.butyl)), 30.4 (s, CH3(tert_butyi)) , 21 .2 (s, p-CH3(mesityi)) , 19.6 (br s, o-CH3(mesityi)) , 18.7 (s, CH3(im ine)) , 18.6 (s, o- [00182] MS (ESI+, CH2CI2): Calculated for C31 H36CI4N4T1, m/z = 464.29 [M-TiCI4]+; Found: 464.30 [M-TiCI4]+ [00183] FTIR (Thin film): vc=N 1599 cm"1 , vc=c 1518 cm"1
[00184] Example 2.7: Dichlorocyclopentadienyl-N-(4-Methylphenyl)-1 ,3- bis(mesityl)imidazol-2-iminecarboxamidotitanium(IV); CpTiCI2[IMesN(CO)N-p-tol]
Figure imgf000084_0001
[00185] To a THF-solution of CpTiCI3 (104 mg, 0.474 mmol) was added dropwise a freshly prepared THF-solution of V-1a (219 mg, 0.477 mmol). The orange solution turned brownish-red upon addition. The volatiles were removed after stirring at room temperature for 1.5 hours. The product was extracted in toluene and passed through a frit containing pressed Celite™. The filtrate was evaporated in vacuo leaving a brownish-red solid.
Recrystallization from toluene-pentane afforded tiny bright red crystals in a 60-70 % yield. CpTiCI2[IMesN(CO)N-p-tol] can also be prepared from IV-2b in an analogous manner. [00186] 1H NMR (400 MHz, 293 K, C6D6) of major species: δ 7.39 (d, J = 8.3 Hz, 2H, o-H p-tolyl), 6.94 (d, J = 8.2 Hz, 2H, m-H p-tolyl) 6.65 (s, 4H, m-H mesityl), 6.18 (s, 5H, C5H5), 5.74 (s, 2H, NCHCHN), 2.12 (s, 12H, 0-CH3 mesityl), 2.09 (s, 3H, CH3 p-tolyl), 2.00 (s, 6H, p-CH3 mesityl) ppm. [00187] 13C NMR (101 MHz, C6D6): δ 161.99 (C=0), 148.66 (NNC=N)), 146.17 (ipso- C p-tolyl), 139.72 (p-C mesityl), 135.87(o-C mesityl), 132.19 (ipso-C mesityl), 131.84 (p-C p- tolyl), 129.65 (m-C mesityl), 128.68 (m-C p-tolyl), 123.77 (o-C p-tolyl), 120.20 (C5H5), 1 17.06 (NCHCHN), 20.98 (p-CH3 mesityl), 20.92 (CH3 p-tolyl), 18.01 (o-CH3 mesityl). [00188] FTIR: vc=01524 cm"1. [00189] Example 2.8: Dichlorobis-N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2- iminecarboxamidotitanium(IV); TiCI2[IMesN(CO)N-p-tol]2 CI
CI
Figure imgf000085_0001
[00190] To a stirring toluene solution of TiCI2(=NtBu)(NHMe2) (1 equiv) in a scintillation vial was added dropwise a toluene solution of compound IV-2b (2 equiv). The yellow solution gradually turned deep red in colour. The reaction was left at room
temperature for 24 h at which time a 1 H NMR spectrum (300 MHz, 293 K, C6D6) of an aliquot was taken. With only 1 resonance in the vinylic region, conversion to product was complete and the reaction mixture was dried in vacuo and the resulting red residue was washed with pentane. After recrystallizing the product from C6H6-pentane and obtaining a dark red solid, the 1 H NMR revealed the f-Bu resonance was gone. The only resonances corresponded to those of the ligand but not the free ligand. Yield: 80-90 %. [00191] 1H NMR (400 MHz, 293 K , C6D6): δ 7.36 (d, J = 8.3 Hz, 2H, o-H p-tolyl), 6.82 (d, J = 8.3 Hz, 2H, m-H p-tolyl), 6.66 (s, 4H, m-H mesityl), 5.72 (s, 2H, NCHCHN), 2.17 (s, 12H, 0-CH3 mesityl), 2.08 (s, 3H, CH3 p-tolyl), 2.04 (s, 6H, p-CH3 mesityl) ppm. [00192] 13C NMR (101 MHz, C6D6) δ 167.17 (C=0), 149.14 (N2C=N), 145.29 (p-C p- tolyl), 139.62 (p-C Mes), 135.47 (ipso-C Mes), 131 .81 (o-C Mes), 130.96 (ipso-C p-tolyl), 129.75 (m-H Mes), 128.53, 128.29, 128.06 (m-C p-tolyl), 122.97 (o-C p-tolyl), 1 16.79 (NCHCHN), 21 .09 (p-CH3 Mes), 20.95 (p-CH3 p-tolyl), 18.06 (o-CH3 Mes) ppm. IR (C=0) 1506 cm-1 . [00193] Anal. Calcd for CseH^C NeCbTi: C, 68.17; H, 6.12; N, 10.96. Found: C, 69.01 ; H, 5.89; N, 10.83. [00194] Example 2.9: Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)] chromium(lll) trichloride
Figure imgf000086_0001
[00195] Method A: To a cold (-78 °C) suspension of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanaminium)]ditosylate (200 mg, 160 mmol) in THF ( 30 mL) was slowly added a solution of NaOfBu (30 mg, 31 1 mmol) in THF (20 mL). The reaction mixture was slowly warmed to RT and then stirred for 4 h. The reaction mixture was filtered and then dried in vacuo for 3h. The crude was dissolved in THF (10 mL) and added drop wise to a stirred solution of CrCI3(THF)3 (56.9 mg, 152 mmol) in THF (5 mL) at room temperature. The colour of the reaction mixture changed to purple and it was allowed to stir over night. The purple solution was filtered, evaporated to dryness, washed with pentane (2 x 5 mL) and dried in vacuo. Yield: 128 mg (79 %) [00196] Method B: To a solution of CrCI3(THF)3 (15 mg, 39 μπιοΙ) in THF (1 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanamine (38 mg, 41 μηιοΓ) at room temperature. The reaction mixture was stirred for overnight. The purple colour solution was filtered, evaporated to dryness and washed with pentane (2 x 3 mL) and dried. Yield: 30 mg (71 %) [00197] Example 2.10: Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)]titanium(lll) trichloride
Figure imgf000086_0002
[00198] Method A: To a cold ( -78 °C) suspension of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanaminium)] ditosylate (170 mg, 135 mmol) in THF ( 20 mL) was slowly added a solution of NaOtBu (26 mg, 264 mmol) in THF (10 mL). The reaction mixture was slowly warmed to RT and then stirred for 4 h. The reaction mixture was filtered and then dried in vacuo for 3h. The crude was dissolved in THF (10 mL) and added drop wise to a stirred solution of TiCI3(THF)3 (48 mg, 129 mmol) in THF (5 mL) at room temperature. The colour of the reaction mixture changed to grey and it was allowed to stir over night. The grey solution was filtered, evaporated to dryness, washed with pentane (2 χ 5 mL) and dried in vacuo to yield pale green solid. Yield: 82 mg (58 %). [00199] Method B: To a stirred solution of TiCU(THF) (18 mg, 48 umol) in THF (1 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanamine (47 mg, 52 μηιοΓ) at room temperature. The reaction mixture was stirred for overnight. The grey colour solution was filtered, evaporated to dryness and washed with pentane (2 x 3 mL) and dried in vacuo to yield pale green solid. Yield: 20.2 mg (40 %) [00200] Example 2.11 : Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)]chromium(ll) dichloride
Figure imgf000087_0001
[00201] Method A: To a cold (-78 °C) suspension of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanaminium)] ditosylate (100 mg, 80 μηιοΓ) in THF (10 mL) was slowly added a solution of NaOfBu (15 mg, 155 mmol) in THF (10 mL). The reaction mixture was slowly warmed to RT and then stirred for 4 h. The reaction mixture was filtered and then dried in vacuo for 3 h. The crude was dissolved in THF (5 mL) and added drop wise to a stirred suspension of CrCI2(THF)2 (20 mg, 76 μηιοΓ) in THF (5 mL) at room temperature. The reaction mixture was allowed to stir for 20 h, filtered and evaporated to dryness. The light green solid was washed with pentane (2 x 5 mL) and dried in vacuo. Yield: 56 mg (72 %) . [00202] Method B: To a suspension of CrCI2(THF)2 (14 mg, 52 μηιοΙ) in THF (2 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6- diisopropylphenyl)imidazolin-2-methanamine (50 mg, 55 μηιοΓ) at room temperature and the reaction mixture was stirred for 20 h. The pale green solution was filtered, evaporated to dryness. The light green solid was washed with pentane (2 x 3 mL) and dried in vacuo. Yield: 42 mg (84 %) [00203] Example 2.12: Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)]iron(ll) dichloride DI PP
D IPP
DI PP
[00204] To a suspension of FeCI2 (4 mg, 33 μηιοΓ) in THF (1 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6-diisopropylphenyl)imidazolin-2- methanamine (30 mg, 33 μηιοΓ) at room temperature and the reaction mixture was stirred for 4 h. The pale yellow solution was filtered, evaporated to dryness and washed with pentane (2 x 3 mL) and dried in vacuo. Yield: 22 mg (64 %) [00205] Example 2.13: Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)]cobalt(ll) dichloride
Figure imgf000088_0001
[00206] To a suspension of CoCI2 (4.3 mg, 33 μηιοΓ) in THF (1 mL) was slowly added a THF (2 mL) solution of pyridine-2-6-bis[1 ,3-bis(2,6-diisopropylphenyl)imidazolin-2- methanamine (30 mg, 33 μηιοΓ) at room temperature and the reaction mixture was stirred for 4 h. The purple solution was filtered, evaporated to dryness and washed with pentane (2 x 5 mL) and dried in vacuo. Yield: 20 mg (58 %). [00207] Example 2.14: Bis(1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2- phenylethenolato))dichlorozirconium(IV); ZrCI2(lmesNAethenolate)2
Figure imgf000088_0002
[00208] A portion of NaHMDS (78.0 mg, 0.4254 mmol) was added as a solid to a THF (5 mL) suspension of compound X-1a (107.6 mg, 0.2079 mmol). The solution immediately turned an intense yellow and the reaction mixture was allowed to stir for 30 minutes. At this time, the solution was filtered through a plug of celite™ and was added to a THF (2 mL) solution of ZrCI4(THF)2 (37.7 mg, 0.0999 mmol). A white ppt formed almost immediately and the slightly yellow solution was allowed to stir for 2 hours. At this time, the solution was filtered and dried under reduced pressure. The product was recrystallized from THF and pentane at -34°C to yield a yellow powder (72.4 mg, 70.94%). [00209] 1H NMR (400 MHz, CDCI3): δ 6.98 (m, 12H, m-CH{mesm + m-CH{phenyl)), 6.88 (d, 2H, p-CH(phenyi)) , 6.74 (d, 4H, θ-ΟΗΜ)), 6.58 (s, 4H, NCHCHN(mesityi)), 5.93 (s, 2H, C=CH-N) 2.30 (s, 12H, p-CH3{mesm), 2.24 (s, 24H, θ-ΟΗ3Μΐ)) ; [00210] 13C{1H) NMR (100 MHz, CDCI3): δ 145.5 (O-C), 139.2 (p-C{mesm), 137.1 (C(phenyl)) , 136.3 (C(mesityl)) , 132.3 (NCN(mesityl)), 129.6 (m-CH(mesityl)), 126.9 (m-CH(phenyl)) , 124.3 (p-CH(phenyl)) , 123.5 (0-CH(phenyl)), 1 17.4 (NCCN(mesityl)) , 1 13.0 (N-C=C), 21 .1 (p-CH3(mesityl)) , 19.2 (0-CH3(mesityl)). [00211] Example 2.15: Cyclopentadienyl-1 ,3-bis(2,4,6-trimethylphenyl)imidazol- 2-imine-N-(2-phenylethenolatodichlorotitanium(IV) CpTiCI2(IMesNAethenolate)
Figure imgf000089_0001
[00212] A portion of NaHMDS (1 13.4 mg, 0.6184 mmol) was added as a solid to a THF (5 mL) suspension of compound Xl-1a (1567.4 mg, 0.3022 mmol). The solution immediately turned an intense yellow and the reaction mixture was allowed to stir for 30 minutes. At this time, the solution was filtered through a plug of celite™ and was added to a THF (2 mL) solution of CpTiCI3 (66.1 mg, 0.3014 mmol). The solution immediately turned a deep, dark ink blue and the reaction mixture was allowed to stir for 2 hours. At this time, the solution was filtered and dried under reduced pressure. The product was recrystallized from THF and pentane at -34°C to yield a dark blue powder (69.8 mg, 37.33%). [00213] 1H NMR (300 MHz, CDCI3): δ 7.08 (m, 6H, m-CH{mesm + m-CH{phenyl)), 7.03 (d, 1 H, p-CH(phenyi)), 6.70 (d, 2H, o-CH(phenyi)), 6.54 (s, 1 H, C=CH-N), 6.46 (s, 2H,
NCHCHN(mesityi)), 6.20 (s, 5H, Cp), 2.34 (s, 6H, p-CH3{mesm), 2.26 (s, 12H,
Figure imgf000089_0002
Example 3: NMR and X-ray Crystal Studies of Ligands 3a and 3b and Coordination Complexes 4a and 5b. [00214] The 1H NMR (CDCI3) spectrum for salt 3a shows characteristic resonances for the mesityl para- and ortho-CH3 protons in a 1 :2 ratio at δ 1.91 and 2.36, respectively. A typical AX2 spectrum for the isopropyl groups in 3b was observed as a set of two doublets at 5 1.12 and 1.06 integrating to 12 protons each and a septet at δ 2.47 integrating to 4 protons, with vicinal coupling of 6.8 Hz observed for all three sets. The resonances arising from the iminic methyl protons were observed at δ 2.1 1 for 3a and at δ 2.75 for 3b. The benzylic protons of the 2,6-dimethylphenyl ring appeared as a singlet at δ 1.60 (3a) and 1.53 (3b), whereas the imidazolium backbone (-NC/-/C/-/N-) protons were observed at the characteristically higher frequencies of δ 6.91 for 3a and 6.95 for 3b, respectively. In the 13C{1H} NMR (CDCI3), the characteristic higher frequency resonances were observed for the exocyclic iminic carbon at δ 162.3 (3a) and 162.1 (3b), while the central imidazolium carbon resonated at δ 146.8 (3a) and 149.7 (3b). [00215] The solid-state structures of 3a and 3b (Figure 1), determined by single- crystal X-ray diffraction studies, are consistent with the solution NMR data. The X-ray data reveals that the 3a and 3b crystallised in the monoclinic space group P2-|/c
Figure imgf000090_0001
[00216] Scheme 4: Proposed Mechanism for the Observed [1 ,3]-Proton Shift in 3a and 3b [00217] The structure was solved using SIR-929 and refined using SHELXTL V6.110 for full-matrix least-squares refinement based on F2. All hydrogen atoms were included in calculated positions and allowed to refine in riding-motion approximation with Uiso-tied to the carrier atom. Hydrogen atoms bound to N4 nitrogen were found in a difference Fourier maps. Thus, N4 rather than N3 is unexpectedly found to be protonated, possibly arising from a 1 ,3-shift of the acidic proton through the formation of a putative four-centre transition state (Scheme 4). Subsequent rotation around the C4-N4 bond would lead to the observed solid- state structures. This [1 ,3]-proton shift also suggests that N4 is significantly more basic than N3. [00218] A comparison of the selected bond lengths and angles are summarised in Table 1. The average C1-N1 and C1-N2 bond lengths for 3a and 3b are shorter than the corresponding bond lengths observed for IPrNH,11 but they are comparable to those observed for the imidazolium salt IMes-HCI and IPr-HCI,12 respectively. This bond shortening arises from delocalisation of the electrons over the whole π-system, which results in the development of a partial positive charge on the five-membered ring and the increase in the bond order between C1 and N3 when compared with IPrNH.11 The wider N1-C1-N2 bond angles observed for the imidazole ring in 3a and 3b, when compared with that for IPrNH11 are also due to the effective stabilisation of the positive charge within the imidazole ring. The presence of the zwitterionic behaviour is further supported by the prominent lengthening of C1-N3 and C4-N4 bonds, when compared with the respective bond lengths reported for IPrNH,11 Ph2C=NPh13 and CAimine HCI.14 [00219] The angles between the best planes formed by the imidazole ring and each of the aryl rings at the 1 ,3-positions are 61.9°, 80.6° (3a) and 70.6°, 80.3° (3b). The angles between the best planes formed by either the imidazole ring or the 2,6-dimethylphenyl group and that passing through C1, N3, C4, C5, N4, C6 are 64.9°, 70.5° (3a) and 72.5°, 74.1 ° (3b), respectively. All the remaining bond lengths and angles are unexceptional and lie within the expected range. [00220] The crystal structure for 4a (Figure 2) shows a distorted octahedral geometry around the titanium(IV) centre. The bond angles around the titanium atom are in the range of 60.50(12) °-177.72(5)°, with the smallest angle attributed to the amidine N3-Ti-N4 bite angle. The lengthening of the C1-N3 and N3-C4 bond to 1.354(5) A and 1.361 (5) A, respectively, and the reduction of the N1-C1-N2 bond angle to 106.5° compared to those observed for 3a are due to the loss of derealization of the electron density over the C1-N3- C4-N4 π-system and are consistent with the coordination of the ligand in a bidentate mode. Furthermore, a greater double bond character for the C4-N4 bond is also supported by the bond length of 1.312(5) A, which is shorter than the values observed for C1-N3 and N3-C4 bonds. This is further evidence of the electron density being predominantly localised over the C1-N3-C4 bonds. The angles between the best plane passing through the
diazametallacycle and either the imidazole ring or the 2,6-dimethylphenyl groups are 56.7° and 80.4°, respectively. The angles between the diazametallacycle and the mesityl groups on either side of the imidazole rings are 64.9° and 76.7°, illustrating the fan-type structure of imidazol-2-imine fragments15 and the shift of the steric bulk from the first to the second coordination sphere. Remaining bond lengths and angles are within the expected range. [00221] Single-crystal X-ray diffraction analysis for 5b shows the unexpected dimeric structure with a perfectly square-planar palladium metal centre bridged by two chloride ligands (Figure 3). The imine imidazol-2-imine ligand is coordinated in a monodentate fashion through N4, in further agreement with our previous observation through the amidinium salts 3a and 3b that the iminic nitrogen N4 is more basic than N3. As expected the bond lengths between the palladium and bridging chloride ligands (2.3335(16) and 2.3413(18) A) are greater than between the metal centre and the terminal chloride CI2 (2.2920(18) A). Attempts to enforce cyclization through the abstraction of a chloride in 5a and 5b with AgBF4, AgPF6 and AgOTf, or through reaction of the free ligand with
[Pd(COD)(CH3CN)CI]BF4 resulted in the formation of palladium black in all cases. [00222] The short C1-N3 bond in 5b (1.313(7) A), compared to that observed in 3b (1.343(5) A), indicates a greater double-bond character for the exocyclic imine of the imidazole-2-imine ring. Structure A (Scheme 2) more closely represents the actual nature of the ligand once coordinated to palladium, despite the slightly elongated C1-N3 bond over that reported for IPrNH.11 This assessment is further supported by the longer C1-N1 and C1- N2 bond in 5b compared to the corresponding ones in 3b. Similarly, the N3-C4 bond in 5b at 1.321 (7) A is also slightly longer than that observed in the precursor salt (1.307(5) A). The N3-C4 and C4-N4 bond length of 1.321 (7) and 1.332(7) A in 5b are consistent with the coordination with palladium, which also results in a more acute C4-N4-C6 bond angle of 1 18.8(5)° in 5b compared to 123.5(3)° observed for 3b. In contrast to that for 3b, the 2,6- diisopropylphenyl rings attached to N1 and N2 in 5b are approximately crystallographically equivalent due to a pseudo-mirror plane that is orthogonal to the imidazole ring and that passes through the exocyclic iminic bond. The angles between the best plane passing through C1, N3, C4, C5, N4, C6 and those formed by the imidazole ring and the 2,6- dimethylphenyl group are 75.6° and 82.4°, respectively. The plane passing through the bimetallic palladium bridge is tilted off by 65.8° from the best plane formed by N3, C4, C5, N4, C6. The remaining bond lengths and bond angles are normal and lie within the expected range. Table 1 Comparison of selected bond lengths (A) and bond angles (deg) for compounds 3a, 3b, 4a and 5b with those reported for IPrNH.11 IMesNAImine HCl IPrNAImine · HCI Ti(IMesNAImine)Cl4
IPrNH" [Pd(IPrNAImine
(3a) (3b) (4a) (5b)
Bond lengths (A)
Cl-Nl, C1-N2 1.3815(15), 1.4004(16) 1.354(4), 1.356(4) 1.353(5), 1.354(5) 1.365(5), 1.349(5) 1.360(7), 1.381(8)
N1-C2, N2-C3 1.382(2), 1.387(2) 1.396(4), 1.397(4) 1.397(5), 1.403(5) 1.386(5), 1.400(5) 1.395(7), 1.401(7)
C2-C3 1.335(2) 1.336(5) 1.345(5) 1.341(6) 1.327(9)
Nl-C„, N2-C„ 1.434(2), 1.433(2) 1.448(4), 1.450(3) 1.450(5), 1.438(5) 1.455(5), 1.449(5) 1.438(7), 1.447(8)
C1-N3 1.289(2) 1.338(4) 1.343(5) 1.354(5) 1.313(7)
C4-N3, C4-N4 - 1.311(4), 1.330(4) 1.307(5), 1.328(5) 1.361(5), 1.312(5) 1.321(7), 1.332(7)
Bond Angles (deg)
N1-C1-N2 104.19(10) 109.0(3) 109.1(3) 106.5(3) 105.7(4)
N1,2-C1-N3 124.05(11), 131.75(11) 123.3(3), 129.6(3) 128.7(3), 123.4(3) 127.2(4), 126.2(4) 124.8(5), 128.7(5)
C1-N3-C4 - 122.7(3) 124.4(3) 122.3(4) 124.2(5)
N3-C4-N4 - 118.8(3) 120.0(3) 110.7(4) 120.3(5)
C4-N4-C6 - 125.3(3) 123.5(3) 122.3(3) 118.8(5)
" Ref 11 Example 4: Ethylene Polymerization
[00223] General Protocol for Ethylene Polymerisation [00224] Polymerisation reactions were carried out in a 500 mL one neck flask equipped with a Chem-Cap valve sidearm at room temperature using the standard procedure detailed below. A vigorously stirred toluene (30 mL) was saturated with ethylene using three freeze-thaw cycles under ethylene atmosphere and then left under one atmosphere of ethylene for 5 min. MAO (10 % in toluene, 4.5 mL, 1000 equiv) was then injected and the mixture was stirred for 5 min. A toluene solution of the respective transition metal complex (10.9 μηιοΙ) was then injected and polymerisation run was carried out for 10 min, unless otherwise stated. After 10 min the toluene/polymer slurry was acidified with 50 % HCI in methanol and the polymer was separated by filtration, washed with methanol, hexane and dried at 70 °C for 24 h. To ensure reproducibility polymerisations were carried out at least twice with each complex and a series of polymerisation runs were performed with charges from the same toluene and MAO batch. [00225] Ethylene Polymerization Activities at room temperature (Average of 2 runs)
Figure imgf000093_0001
Figure imgf000093_0002
Figure imgf000094_0001
Figure imgf000095_0001
[00226] Although the invention has been described with reference to certain specific embodiments, various modifications thereof will be apparent to those skilled in the art without departing from the purpose and scope of the invention as outlined in the claims appended hereto. For example, the substitution of phosphorous for nitrogen as an electron donor in a catalyst ligand has been demonstrated, as described above. [00227] Any examples provided herein are included solely for the purpose of illustrating the invention and are not intended to limit the invention in any way. Any drawings provided herein are solely for the purpose of illustrating various aspects of the invention and are not intended to be drawn to scale or to limit the invention in any way. The disclosures of all prior art recited herein are incorporated herein by reference in their entirety. References: [00228] 1 . Nolan, S. P. Synthesis of 1 ,3-distributed imidazolium salts via condensation of methylaniline with glyoxal and cyclization with paraformaldehyde. US 7109348 B1 , September 19, 2006. [00229] 2. Arduengo, A. J., Ill; Krafczyk, R.; Schmutzler, R.; Craig, H. A.;
Goerlich, J. R.; Marshall, W. J.; Unverzagt, M., Tetrahedron 1999, 55, 14523-14534. [00230] 3. Tamm, M.; Petrovic, D.; Randoll, S.; Beer, S.; Bannenberg, T.; Jones, P. G.; Grunenberg, J., Org. Biomol. Chem. 2007, 5, 523-530. [00231] 4. Andrews, M. A.; Chang, T. C. T.; Cheng, C. W. F.; Emge, T. J.; Kelly, K. P.; Koetzle, T. F., J. Am. Chem. Soc. 1984, 106, 5913-5920. [00232] 5. Drew, D.; Doyle, J. R., Inorg. Synth. 1990, 28, 346-349. [00233] 6. Shi, M.; Jiang, J.-K.; Cui, S.-C, Tetrahedron 2001 , 57, 7343-7347. [00234] 7. Brindley, J. C; Caldwell, J. M.; Meakins, G. D.; Plackett, S. J.; Price, S. J., J. Chem. Soc, Perkin Trans. 1 1987, 1 153-1 158. [00235] 8. Johnson, L. K. Iron or cobalt complex catalyst for polymerization of ethylene. WO 0066638, November 9, 2000. [00236] 9. Altomare, A.; Carascano, G.; Giacovazzo, C; Guagliardi, A.; Burla, M.C.; Polidori, G.; Camalli, M. J. App. Cryst., 1994, 27, 435. [00237] 10. Sheldrick, G.; Acta Crys. A: Found. Crystallogr., 2008, 64, 1 12. [00238] 1 1 . Panda, T.K.; Trambitas, A.G.; Bannenberg, T.; Hrib, C.G.; Randoll, S.; Jones, P.G.; Tamm, M. Inorg. Chem., 2009, 48, 5462. [00239] 12. Arduengo III, A.J.; Krafczyk, R.; Schmutzler, R.; Craig, H.A.; Goerlich, J.R.; Marshall, W.J.; Unverzagt, M. Tetrahedron, 1999, 55, 14523. [00240] 13. Tucker, A; Hoekstra, A; Ten Carte, J.M.; Vos, A. Acta Crystallogr., 1975, 31 , 733. [00241] 14. Badaj, A.C.; Dastgir, S.; Lough, A.J.; Lavoie, G.G. Dalton Trans., 2010, 39, 3361 ; Coleman, K.S.; Dastgir, S.; Barnett, G.; Alvite, M.J. P.; Cowley, A.R.; Green, M.L.H. J. Organomet. Chem., 2005, 690, 5591 . [00242] 15. Hillier, A.C.; Sommer, W.J. ; Yong, B.S.; Petersen, J. L; Cavallo, L; Nolan, S.P.; Organometallics, 2003, 22, 4322; Scott, N.M.; Nolan, P. Eur. J. Inorg. Chem., 2005, 2005, 1815. [00243] 16. Petrovic, D.; Bannenberg, T.; Randoll, S.; Jones, P.G.; Tamm, M., Dalton Transactions, 2007, 2812-2822. [00244] 17. Petrovic, D.; Hill, L.M.R.; Jones, P.G.; Tolman, W.B.; Tamm, M., Dalton Transactions, 2008, 887-894. [00245] Beuken van den, Esther K.; Smeets, Wilbreth J. J.; Spek Anthony L; Feringa, Ben L, Chem, Commun., 1998, 223-224. [00246] Daugulis, 0.;Brookhart M. Organometallics, 2002, 5926-5934. [00247] Guan, Zhubin; Organometicallics, 2002, 3580-3586. [00248] Gates, Derek P.; Svejda, Steven A.; Onate, Enrique; Killian, Christopher M.; Johnson K. Lynda; White, Peter S.; Brookhart, Maurice, Macromolecules, 2000, 22, 23202334. [00249] Tempel, Daniel J.; Johnson Lynda K.; Huff, R. Leigh, White, Peter S;
Brookhart, Maurice. J, Am. Chem Soc. 2000, 122, 6686-6700

Claims

WE CLAIM:
1. A compound according to formula (I):
Figure imgf000098_0001
I
wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring;
R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R21 is selected from hydrocarbyl, and substituted hydrocarbyl;
R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R20 and R21 may be taken together with E4 and N2 to form a ring; when R20 and R21 together with E4 and N2 form a ring, the ring may be further substituted with 1 to 4 substituents wherein the substituents are hydrocarbyl, substituted hydrocarbyl, heteroatom substituted hydrocarbyl or substituted heteroatom substituted hydrocarbyl, and when the ring is substituted with a substituted heteroatom substituted hydrocarbyl, and if the substitutent on the heteroatom substituted hydrocarbyl is C6.14 aryl the substituent may be further substituted by up to 3 Ci-6 alkyl groups;
R20 and R22 may be taken together with C2 and E4 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulfur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E4 is selected from carbon and phosphorus;
E5 is selected from carbon and boron;
E2 and E3 may be connected by either a single bond or a double bond;
X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate B(C6F5)4 ", 3,5-(C6H3)- (CF3)2 ~, or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1 ; m is 1 or 2 and is chosen to obey the valency of E4; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; g is g is 0, 1 , 2 and is chosen to obey the valency of C2; q is 0, 1 or 2; and with the proviso that the ligand is not 2,6-bis[1 ,3-di-fe/f-butylimidazolin-2- imino)methyl]pyridine.
A compound according to formula (II):
Figure imgf000100_0001
II
wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring;
R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl;
R20 and R24 may be taken together with E4 and E10 to form a ring;
R20 and R22 may be taken together with C2 and E4 to form a ring;
R23 and R24 can be taken together with E10 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulfur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E4 is carbon;
E5 is selected from carbon and boron;
E10 is selected from nitrogen and phosphorous;
E2 and E3 may be connected by either a single bond or a double bond;
X" is chloride, bromide, iodide, BF4-, PF6-, tosylate, mesylate, B(C6F5)4-, 3,5-(C6H3)- (CF3)2- or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1; m is 1 or 2 and is chosen to obey the valency of E4; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2.
3. A compound according to formula (III):
Figure imgf000102_0001
III
wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom-substituted hydrocarbyl;
R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R20 and R23 may be taken together with E4 and E10 to form a ring;
R20 and R22 may be taken together with C2 and E4 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulfur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E4 is carbon;
E5 is selected from carbon and boron;
E10 is selected from nitrogen and phosphorous;
E2 and E3 may be connected by either a single bond or a double bond;
M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1; m is 1 or 2 and is chosen to obey the valency of E4; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; and g is 0, 1 , 2 and is chosen to obey the valency of C2.
4. A compound according to formula (IV):
Figure imgf000104_0001
IV
wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached
heteroatom-substituted hydrocarbyl;
R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl;
R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R22 and R25 may be taken together with C2, C3 and E6 to form a ring;
R25 and R23 may be taken together with E6, C3, and N2 to form a ring;
R23 and R24 can be taken together with N2 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached
heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulfur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E5 is selected from carbon and boron;
E6 is selected from oxygen, sulfur and nitrogen;
E2 and E3 may be connected by either a single bond or a double bond; X is chloride, bromide, iodide, BF4-, PF6-, tosylate, mesylate, B(C6F5)4-, 3,5-(C6H3)- (CF3)2- or other common anions; i is 0 or 1 ; when i = 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; g is 0, 1 or 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2.
5. A compound according to formula (V):
Figure imgf000106_0001
wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl; R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring;
R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R23 and R25 can be taken together with N2, C3 and E6 to form a ring;
R22 and R25 can be taken together with C2, C3 and E6 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached
heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from either nitrogen, oxygen and sulfur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E5 is selected from carbon and boron;
E6 is selected from oxygen, sulfur and nitrogen;
E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when i = 0, E2 and E5 may either not be connected by any bond, or alternatively, may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; and g is 0, 1 or 2 and is chosen to obey the valency of C2.
6. A compound according to formula (VI):
Figure imgf000108_0001
VI
wherein,
R and R are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring; R is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R23 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached
heteroatom-substituted hydrocarbyl;
R25 is selected from hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R23 and R25 can be taken together with N2, C3 and E6 to form a ring;
R22 and R25 can be taken together with C2, C3 and E6 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached
heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulfur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E5 is selected from carbon and boron;
E6 is selected from oxygen, sulfur and nitrogen;
E2 and E3 may be connected by either a single bond or a double bond;
M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 , when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1 and E6; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; and g is 0, 1 or 2 and is chosen to obey the valency of C2.
7. The compound according to formula (VII)
Figure imgf000110_0001
VII wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring;
R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl; R20 and R22 may be taken together with C2 and E4 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulphur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E4 is selected from carbon, phosphorus and sulfur;
E5 is selected from carbon and boron;
E2 and E3 may be connected by either a single bond or a double bond;
X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)- (CF3)2 " or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1; m is 1 or 2 and is chosen to obey the valency of E4; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2.
8. A compound according to formula (VIII)
Figure imgf000112_0001
VIII wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring;
R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R24 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, heteroatom-attached heteroatom-substituted hydrocarbyl, silicon-attached hydrocarbyl, and tin-attached hydrocarbyl;
R20 and R24 may be taken together with E4 and O to form a ring; R20 and R22 may be taken together with C2 and E4 to form a ring; G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulphur;
E2 is selected from carbon, nitrogen, oxygen, sulfur and boron;
E3 is selected from carbon, nitrogen, oxygen and sulfur;
E4 is selected from carbon and phosphorus;
E5 is selected from carbon and boron;
E2 and E3 may be connected by either a single bond or a double bond;
X" is chloride, bromide, iodide, BF4 ", PF6 ", tosylate, mesylate, B(C6F5)4 ", 3,5-(C6H3)- (CF3)2 " or other common anions; i is 0 or 1 ; when i is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1; m is 1 or 2 and is chosen to obey the valency of E4; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; g is 0, 1 , 2 and is chosen to obey the valency of C2; and q is 0, 1 or 2. The compound according to form
Figure imgf000114_0001
IX wherein,
R10 and R13 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-substituted hydrocarbyl;
R11 and R12 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R11 and R12 may be taken together with E2, E5 and G2to form a ring;
R20 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl and heteroatom-attached heteroatom-substituted hydrocarbyl;
R22 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
R20 and R22 may be taken together with C2 and E4 to form a ring;
G2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-substituted hydrocarbyl, heteroatom-attached hydrocarbyl, and heteroatom-attached heteroatom-substituted hydrocarbyl;
G2 and E2 may be connected by either a single bond or a double bond;
G2 and E5 may be connected by either a single bond or a double bond;
E1 is selected from nitrogen, oxygen and sulphur; E2 is selected from carbon, nitrogen, oxygen, sulfur and boron; E3 is selected from carbon, nitrogen, oxygen and sulfur; E4 is selected from carbon and phosphorus; E5 is selected from carbon and boron;
E2 and E3 may be connected by either a single bond or a double bond; M+ is sodium, potassium, lithium or thallium cation; i is 0 or 1 ; when I is 0, E2 and E5 may either not be connected by any bond, or may be connected by a single bond or a double bond; j is 0, 1 or 2; when j is 2, the carbon atoms between N1 and E4 are connected to each other by either single, double or triple bonds; k is 0 or 1 and is chosen to obey the valency of E1; m is 1 or 2 and is chosen to obey the valency of E4; n is 0, 1 , 2 and is chosen to obey the valency of E2, E3 and E5; and g is 0, 1 , 2 and is chosen to obey the valency of C2.
10. The compound according to any one of claims 1 to 9 wherein E2 and E5 are carbon;
E1 and E3 are nitrogen.
1 1. The compound according to any one of claims 1 to 10 that is:
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- imine hydrochloride;
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2- imine hydrochloride; N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-di-tert-butylimidazol-2-im
hydrochloride;
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- imine;
N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2- imine;
N-(2-iodo-1-(4-chlorophenyl)ethylidene)-2,4,6-trimethylaniline;
N-(2-(mesitylimino)-2-(4-chlorophenyl)ethyl))-1 ,3-bis(2,4,6-trimethylphen- yl)imidazol-2-imine hydroiodide;
N-(4-Methylphenyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-iminecarboxamide; N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarboxamide;
N-(4-Methylphenyl)-N-trimethylsNyl-1 ,3-bis(mesityl)imidazol-2-iminecarboxamid Lithium N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarboxamide;
Pyridine-2-6-bis[1 ,3-bis(2,4,6-trimethylphenyl)imidazolin-2-methanaminium)] ditosylate; Pyridine-2-6-bis[1 ,3-bis(2,6-diisopropylphenyl)imidazolin-2- methanaminium)] ditosylate;
N-(2-oxo-2-phenylethyl))-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine hydrobromide;
N-(2-oxo-2-phenylethyl))-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine or Sodium 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2-phenylethenolate).
A use of a compound according to any of claims 1 to 1 1 as a ligand or ligand
13. A coordination complex comprising a compound as defined in any one of claims 1 to 1 1 as a ligand and a metal chosen from lUPAC Group 2 through 12, including lanthanides.
14. The coordination complex according to claim 13 wherein the metal is Ni, Pd, Pt, Fe, Co, Y, Ti, Zr, V, Hf, Cr, Mn, Ru, Rh, Re, Os, Ir, Cu, Mg, Zn or a lanthanide metal. The coordination complex according to any one of claims 13 to 14 wherein there are two ligands per metal atom.
The coordination complex according to any one of claims 13 to 15 wherein the ligand
17. The coordination complex according to any one of claims 13 to 16 that is:
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine teterachlorotitanium(IV);
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-imine teterachlorotitanium(IV);
/V-(1-ethylimino-2,6-dimethylphenyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- iminedichloropalladium(ll) dimer;
N-(1-(2,6-Dimethylphenylimino)ethyl)-1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-imine dichloropalladium(ll) dimmer; /V-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine)- ferf-butylimidodichlorotitanium(IV);
N-(1-(2,6-dimethylphenylimino)ethyl)-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine)- (2-tert-butylphenylimido)dichlorotitanium(IV);
Dichlorocyclopentadienyl-N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarbox- amidotitanium(IV);
Dichlorobis-N-(4-Methylphenyl)-1 ,3-bis(mesityl)imidazol-2-iminecarboxamido- titanium(IV);
Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-methanamine)] chromium(lll) trichloride; Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-methanamin
trichloride;
Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2- methanamine)]chromium(ll) dichloride;
Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-m
dichloride;
Pyridine-2-6-bis[1 ,3-bis(2,6-diisoprpylphenyl)imidazolin-2-methanamine)]cobalt(ll) dichloride;
Bis(1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2- phenylethenolato))dichlorozirconium(IV); or
Cyclopentadienyl-1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-imine-N-(2- phenylethenolatodichlorotitanium(IV).
18. A use of a coordination complex according to any one of claims 13 to 17 as a catalyst.
19. The use according to claim 18 wherein the catalyst is used to catalyze a polymerization reaction or a copolymerization reaction.
20. The use according to claim 19 wherein the polymerization or copolymerization reaction includes monomers selected from acrylates, vinylacetate, lactides and lactones.
21. The use according to claim 18 wherein the catalyst is used to catalyze a reaction selected from cross-coupling reaction, hydroformylation, hydrogenation, hydrosylilation and hydroboration.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8907031B2 (en) 2011-04-20 2014-12-09 Chevron Phillips Chemical Company Lp Imino carbene compounds and derivatives, and catalyst compositions made therefrom
KR101547428B1 (en) 2014-06-30 2015-08-25 경북대학교 산학협력단 Zinc complex catalyst for polymerization of ring ester monomers, catalyst composition including the zinc complex catalyst, method of preparing the zinc complex catalyst, and method of preparing a polymer using the zinc complex catalyst
JP2017502934A (en) * 2013-12-19 2017-01-26 ダウ グローバル テクノロジーズ エルエルシー Metal-ligand complex, olefin polymerization catalyst derived therefrom, and olefin polymerization method using the catalyst
CN113735896A (en) * 2020-05-27 2021-12-03 广西师范大学 Method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting monoatomic palladium-phosphine ligand

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Title
DASTGIR ET AL.: 'Coordination study of a new class of imine imidazol-2-imine ligands to titanium(IV) and palladium(II)' DALTON TRANSACTIONS vol. 39, 2010, pages 6943 - 6946 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8907031B2 (en) 2011-04-20 2014-12-09 Chevron Phillips Chemical Company Lp Imino carbene compounds and derivatives, and catalyst compositions made therefrom
JP2017502934A (en) * 2013-12-19 2017-01-26 ダウ グローバル テクノロジーズ エルエルシー Metal-ligand complex, olefin polymerization catalyst derived therefrom, and olefin polymerization method using the catalyst
KR101547428B1 (en) 2014-06-30 2015-08-25 경북대학교 산학협력단 Zinc complex catalyst for polymerization of ring ester monomers, catalyst composition including the zinc complex catalyst, method of preparing the zinc complex catalyst, and method of preparing a polymer using the zinc complex catalyst
CN113735896A (en) * 2020-05-27 2021-12-03 广西师范大学 Method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting monoatomic palladium-phosphine ligand
CN113735896B (en) * 2020-05-27 2024-05-24 广西师范大学 Method for preparing Z-configuration-1, 2-ditin substituted olefin by adopting monoatomic palladium phosphine ligand

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