WO2005035121A2 - Complexes metallliques a base de schiff utilisables comme catalyseurs en synthese organique - Google Patents

Complexes metallliques a base de schiff utilisables comme catalyseurs en synthese organique Download PDF

Info

Publication number
WO2005035121A2
WO2005035121A2 PCT/BE2004/000146 BE2004000146W WO2005035121A2 WO 2005035121 A2 WO2005035121 A2 WO 2005035121A2 BE 2004000146 W BE2004000146 W BE 2004000146W WO 2005035121 A2 WO2005035121 A2 WO 2005035121A2
Authority
WO
WIPO (PCT)
Prior art keywords
group
thio
alkyl
ligand
metal complex
Prior art date
Application number
PCT/BE2004/000146
Other languages
English (en)
Other versions
WO2005035121A3 (fr
Inventor
Francis Walter Cornelius Verpoort
Tom Opstal
Original Assignee
Universiteit Gent
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universiteit Gent filed Critical Universiteit Gent
Publication of WO2005035121A2 publication Critical patent/WO2005035121A2/fr
Publication of WO2005035121A3 publication Critical patent/WO2005035121A3/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/546—Metathesis reactions, e.g. olefin metathesis alkyne metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to transition metal complexes which are useful as catalyst components, either alone or in combination with co-catalysts or initiators, in a wide variety of organic synthesis reactions including olefin metathesis, acetylene metathesis and reactions involving the transfer of an atom or group to an ethylenically or acetylenically unsaturated compound or another reactive substrate, such as atom transfer radical polymerisation, atom transfer radical addition, vinylation, cyclopropanation of ethylenically unsaturated compounds, epoxidation, oxidative cyclisation, aziridination, cyclopropenation of alkynes, Diels-Alder reactions, Michael addition, aldol condensation of ketones or aldehydes, Robinson annulation, hydroboration, hydrosilylation, hydrocyanation of olefins and alkynes, allylic alkylation, Grignard cross-coupling, oxidation of organic compounds (including saturated hydrocarbons, sulf
  • the present invention also relates to methods for making said transition metal complexes and to novel intermediates involved in such methods.
  • the present invention also relates to obtaining polymers with extremely narrow molecular weight distribution by means of a living polymerisation reaction.
  • the present invention further relates to certain derivatives of the said metal complexes which are suitable for covalent bonding to a carrier, the product of such covalent bonding being useful as a supported catalyst for heterogeneous catalytic reactions.
  • the present invention relates to certain Schiff base complexes of metals such as ruthenium and their use as catalysts for ring-opening metathesis polymerisation of cyclic olefins, atom transfer radical polymerisation of styrenes or (met )acrylic esters, and for quinoline synthesis.
  • Olefin metathesis is a catalytic process including, as a key step, a reaction between a first olefin and a first transition metal alkylidene complex, thus producing an unstable intermediate metallacyclobutane ring which then undergoes transformation into a second olefin and a second transition metal alkylidene complex according to equation (1) hereunder. Reactions of this kind are reversible and in competition with one another, so the overall result heavily depends on their respective rates and, when formation of volatile or insoluble products occur, displacement of equilibrium.
  • Equation 2 Of potentially greater interest than homo-coupling (equation 2) is cross-coupling between two different terminal olefins. Coupling reactions involving dienes lead to linear and cyclic dimers, oligomers, and, ultimately, linear or cyclic polymers (equation 3). In general, the latter reaction called acyclic diene metathesis (hereinafter referred to as ADMET) is favoured in highly concentrated solutions or in bulk, while cyclisation is favoured at low concentrations.
  • ADMET acyclic diene metathesis
  • RCM ring- closing metathesis
  • Strained cyclic olefins can be opened and oligomerised or polymerised (ring opening metathesis polymerisation, hereinafter referred to as ROMP, shown in equation 5).
  • ROMP ring opening metathesis polymerisation
  • the alkylidene catalyst reacts more rapidly with the cyclic olefin (e.g. a norbornene or a cyclobutene) than with a carbon-carbon double bond in the growing polymer chain, then a "living ring opening metathesis polymerisation" may result, i.e. there is little termination during or after the polymerization reaction.
  • a large number of catalyst systems comprising well-defined single component metal carbene complexes have been prepared and utilized in olefin metathesis.
  • Remaining problems to be solved with the carbene complexes of Grubbs are (i) improving both catalyst stability (i.e. slowing down decomposition) and metathesis activity at the same time and (ii) broadening the range of organic products achievable by using such catalysts, e.g. providing ability to ring-close highly substituted dienes into tri- and tetra-substituted olefins.
  • living polymerisation systems were reported for anionic and cationic polymerisation, however their industrial application has been limited by the need for high-purity monomers and solvents, reactive initiators and anhydrous conditions. In contrast, free-radical polymerisation is the most popular commercial process to yield high molecular weight polymers.
  • a large variety of monomers can be polymerised and copolymerised radically under relatively simple experimental conditions which require the absence of oxygen but can be carried out in the presence of water.
  • free-radical polymerisation processes often yield polymers with ill- controlled molecular weights and high polydispersities. Combining the advantages of living polymerisation and radical polymerisation is therefore of great interest and was achieved by the atom (or group) transfer radical polymerisation process (hereinafter referred as ATRP) of U.S. Patent No. 5,763,548 involving (1) the atom or group transfer pathway and (2) a radical intermediate.
  • ATRP atom transfer radical polymerisation process
  • This type of living polymerization wherein chain breaking reactions such as transfer and termination are substantially absent, enables control of various parameters of the macromolecular structure such as molecular weight, molecular weight distribution and tenninal functionalities. It also allows the preparation of various copolymers, including block and star copolymers.
  • Living/controlled radical polymerization requires a low stationary concentration of radicals in equilibrium with various dormant species. It makes use of novel initiation systems based on the reversible formation of growing radicals in a redox reaction between various transition metal compounds and initiators such as alkyl halides, aralkyl halides or haloalkyl esters.
  • ATRP is based on a dynamic equilibrium between the propagating radicals and the dormant species which is established through the reversible transition metal-catalysed cleavage of the covalent carbon- halogen bond in the dormant species.
  • Polymerisation systems utilising this concept have been developed for instance with complexes of copper, ruthenium, nickel, palladium, rhodium and iron in order to establish the required equilibrium. Due to the development of ATRP, further interest appeared recently for the Kharash addition reaction, consisting in the addition of a polyhalogenated alkane across an olefin through a radical mechanism (first published by Kharash et al.
  • ATRP Atom Transfer Radical Addition
  • telogens a wide range of internal, terminal and cyclic olefins and diolefins were tested with a wide range of polyhalides including fluoro, chloro, bromo and iodo as halogen atoms, as described for instance in Eur. Polym. J. (1980) 16:821 and Tetrahedron (1972) 28:29.
  • M is a metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table, preferably a metal selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, nickel and cobalt;
  • Z is selected from the group consisting of oxygen, sulphur, selenium, NR"", PR"", AsR"" and SbR”";
  • R", R"' and R"" are each a radical independently selected from the group consisting of hydrogen, C ⁇ alkyl.
  • R' is either as defined for R", R"' and R"" when included in a compound having the general formula (IA) or, when included in a compound having the general formula (IB), is selected from the group consisting of C ⁇ alkylene and C 3 .
  • R is a constraint steric hindrance group having a pKa of at least about 15
  • R 2 is an anionic ligand
  • R 3 and R 4 are each hydrogen or a radical selected from the group consisting of C 1-20 alkyl, C2- 2 0 alkenyl, C 2 - 2 o alkynyl, C ⁇ -20 carboxylate, C 1-20 alkoxy, C 2 . 2 o alkenyloxy, C 2 .
  • R' and one of R 3 and R 4 may be bonded to each other to form a bidentate ligand; R'" and R"" may be bonded to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorous, arsenic and antimony; R and R 4 together may form a fused aromatic ring system, and y represents the number of sp 2 carbon atoms between M and the carbon atom bearing R 3 and R 4 and is an integer from 0 to 3 inclusive, salts, solvates and enantiomers thereof.
  • reaction-injection molding processes such as, but not limited to, the bulk polymerisation of endo- or exo-dicyclopentadiene, or formulations thereof.
  • WO 93/20111 describes osmium- and ruthenium-carbene compounds with phosphine ligands as purely thermal catalysts for ring-opening metathesis polymerization of strained cycloolefins, in which cyclodienes such as dicyclopentadiene act as catalyst inhibitors and cannot be polymerized. This is confirmed for instance by example 3 of U.S. Patent No.
  • the present invention is based on a first unexpected finding that efficient olefin metathesis catalysts can be obtained from metal complexes, in particular ruthenium complexes, which do not include an alkylidene ligand.
  • Other unexpected findings of the invention are that efficient olefin metathesis catalysts can also be obtained by coordinating a metal such as ruthenium with: - specifically substituted tetradentate ligands comprising two Schiff bases linked through a linking group having strongly electron-withdrawing substituents, or a combination of two anionic ligands, a non-anionic unsaturated ligand and an aliphatic saturated monoamine.
  • novel metal complexes as well as some known metal complexes, either used as such or supported onto a carrier, are efficient catalysts in organic synthesis reactions such as acetylene metathesis and reactions involving the transfer of an atom or group to an ethylenically or acetylenically unsaturated compound or another reactive substrate, such as atom transfer radical polymerisation or addition, vinylation, cyclopropanation of ethylenically unsaturated compounds, quinoline synthesis, epoxidation, oxidation of organic compounds (including saturated hydrocarbons, sulfides, selenides, phosphines and aldehydes), cyclopropenation of alkynes, hydrocyanation of olefins and alkynes, hydrosilylation of olefins or alkynes or ketones, aziridination of olefins, hydroamidation, hydrogenation of olefins or ketones, aminolysis of olef
  • Figure 1 schematically shows the general formulae (IA) and (IB) of bidentate Schiff base ligands that are suitable for coordination in metal complexes according to an embodiment of the present invention.
  • Figure 2 schematically shows the general formulae (IIA), (MB) and (IIC) of tetradentate ligands having two Schiff bases that are suitable for coordination in metal complexes according to another embodiment of the present invention.
  • Figure 3 schematically shows the general formulae (IIIA) and (IIIB) of tetradentate Schiff base ligands and the general formula (NIC) of bidentate ligands that are suitable for coordination in metal complexes according to another embodiment of the present invention.
  • Figure 4 shows the proton nuclear magnetic resonance spectrum of a Schiff base ligand that is suitable for coordination in the metal complexes according to an embodiment of the present invention.
  • Figure 5 schematically shows the general formula (IV) of tridentate Schiff base ligands that are suitable for coordination in metal complexes according to another embodiment of the present invention.
  • Figure 6 schematically shows general formulae (V) and (VI) of pyrrolaldimine ligands that are suitable for coordination in metal complexes according to another embodiment of the present invention.
  • the term complex, or coordination compound refers to the result of a donor-acceptor mechanism or Lewis acid-base reaction between a metal (the acceptor) and several neutral molecules or ionic compounds called ligands, each containing a non-metallic atom or ion (the donor).
  • Ligands that have more than one atom with lone pairs of electrons (i.e. more than one point of attachment to the metal center) and therefore occupy more than one coordination site are called multidentate ligands. The latter, depending upon the number of coordination sites occupied, include bidentate, tridentate and tetradentate ligands.
  • the term " monometallic" refers to a complex in which there is a single metal center.
  • the term “ heterobimetallic” refers to a complex in which there are two different metal centers.
  • the term “ homobimetallic” refers to a complex having two identical metal centers, which however need not have identical ligands or coordination number.
  • metal refers to a transition metal belonging to any of groups 4,
  • Periodic Table such as, but not limited to, iridium, ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt.
  • C ⁇ - alkyl means straight and branched chain saturated acyclic hydrocarbon monovalent radicals having from 1 to 7 carbon atoms such as, for example, methyl, ethyl, propyl, n-butyl, 1-methylethyl (isopropyl), 2-methylpropyl (isobutyl), 1 ,1-dimethylethyl (ter-butyl), 2-methylbutyl, n-pentyl, dimethylpropyl, n- hexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl and the like; optionally the carbon chain length of such group may be extended to 20 carbon atoms.
  • substituting radical and unless otherwise stated, the term “C ⁇ - alkyl”
  • C 1-7 alkylene means the divalent hydrocarbon radical corresponding to the above defined C 1- alkyl, such as methylene, bis(methylene), tris(methylene), tetramethylene, hexamethylene and the like.
  • C 3 . 10 cycloalkyl mean a mono- or polycyclic saturated hydrocarbon monovalent radical having from 3 to
  • C 3-10 cycloalkyl-alkyl refers to an aliphatic saturated hydrocarbon monovalent radical (preferably a C -7 alkyl such as defined above) to which a C 3 . 0 cycloalkyl (such as defined above) is already linked such as, but not limited to, cyclohexylmethyl, cyclopentylmethyl and the like.
  • C 3 _ 10 cycloalkylene means the divalent hydrocarbon radical corresponding to the above defined C 3-10 cycloalkyl, such as 1 ,2-cyclohexylene and 1,4-cyclohexylene.
  • aryl designates any mono- or polycyclic aromatic monovalent hydrocarbon radical having from 6 up to 30 carbon atoms such as but not limited to phenyl, naphthyl, anthracenyl, phenantracyl, fluoranthenyl, chrysenyl, pyrenyl, biphenylyl, terphenyl, picenyl, indenyl, biphenyl, indacenyl, benzocyclobutenyl, benzocyclooctenyl and the like, including fused benzo-C 4-3 cycloalkyl radicals (the latter being as defined above) such as, for instance, indanyl, tetrahydronaphtyl, fluorenyl and the like, all of the said radicals being optionally substituted with one or more substituents selected from the group consisting of halogen, amino,
  • arylene means the divalent hydrocarbon radical corresponding to the above defined aryl, such as " phenylene, naphtylene and the like.
  • homocyclic means a mono- or polycyclic, saturated or mono- unsaturated or polyunsaturated hydrocarbon radical having from 4 up to 15 carbon atoms but including no heteroatom in the said ring; for instance the said combination forms a C 2 _ 6 alkylene radical, such as tetramethylene, which cyclizes with the carbon atoms to which the said two substituting hydrocarbon radicals are attached.
  • heterocyclic means a mono- or polycyclic, saturated or mono-unsaturated or polyunsaturated monovalent hydrocarbon radical having from 2 up to 15 carbon atoms and including one or more heteroatoms in one or more heterocyclic rings, each of said rings having from 3 to 10 atoms (and optionally further including one or more heteroatoms attached to one or more carbon atoms of said ring, for instance in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and/or to one or more heteroatoms of said ring, for instance in the form of a sulfone, sulfoxide, N-oxide, phosphate, phosphonate or selenium oxide group), each of said heteroatoms being independently selected from the group consisting of nitrogen, oxygen, sulfur, selenium and phosphorus, also including radicals wherein
  • each carbon atom of said heterocyclic ring may be independently substituted with a substituent selected from the group consisting of halogen, nitro, C 1-7 alkyl (optionally containing one or more functions or radicals selected from the group consisting of carbonyl (oxo), alcohol (hydroxyl), ether (alkoxy), acetal, amino, imino,
  • heterocyclic radicals may be sub-divided into heteroaromatic (or " heteroaryl") radicals and non-aromatic heterocyclic radicals; when a heteroatom of the said non-aromatic heterocyclic radical is nitrogen, the latter may be substituted with a substituent selected from the group
  • cycloalkyl refers to substituents wherein a C ⁇ _ 7 alkyl, C 2-7 alkenyl or C 2-7 alkynyl (optionally the carbon chain length of such groups may be extended to 20 carbon atoms), respectively a C 3 .
  • cycloalkyl, aryl, arylalkyl or heterocyclic radical are attached to an oxygen atom or a divalent sulfur atom through a single bond, such as but not limited to methoxy, ethoxy, propoxy, butoxy, pentoxy, isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiocyclopropyl, thiocyclobutyl, thiocyclopentyl, thiophenyl, phenyloxy, benzyloxy, mercaptobenzyl, cresoxy and the like.
  • halogen means any atom selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • halo C 1-7 alkyl means a C 1-7 alkyl radical (such as above defined, i.e.
  • the carbon chain length of such group may be extended to 20 carbon atoms) in which one or more hydrogen atoms are independently replaced by one or more halogens (preferably fluorine, chlorine or bromine), such as but not limited to difluoromethyl, trifluoromethyl, trifluoroethyl, octafluoropentyl, dodecafluoroheptyl, dichloromethyl and the like.
  • halogens preferably fluorine, chlorine or bromine
  • alkenyl means a straight or branched acyclic hydrocarbon monovalent radical having one or more ethylenical unsaturations and having from 2 to 7 carbon atoms such as, for example, vinyl, 1-propenyl, 2-propenyl (allyl), 1-butenyl, 2-butenyl, 2-pentenyl, 3-pentenyl, 3- methyl-2-butenyl, 3-hexenyl, 2-hexenyl, 2-heptenyl, 1 ,3-butadienyl, pentadienyl, hexadienyl, heptadienyl, heptatrienyl and the like, including all possible isomers thereof; optionally the carbon chain length of such group may be extended to 20 carbon atoms.
  • C 3 _ ⁇ 0 cycloalkenyl means a monocyclic mono- or polyunsaturated hydrocarbon monovalent radical having from 3 to 8 carbon atoms, such as for instance cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cycloheptadienyl, cycloheptatrienyl, cyclooctenyl, cyclooctadienyl, cyclooctatrienyl, 1 ,3,5,7- cyclooctatetraenyl and the like, or a C 7- o polycyclic mono- or polyunsaturated hydrocarbon monovalent radical having from 7 to 10 carbon atoms such as dicyclopentadieny
  • arylalkyl refers to an aliphatic saturated or ethylenically unsaturated hydrocarbon monovalent radical (preferably a C 1-7 alkyl or C 2-7 alkenyl radical such as defined above, i.e.
  • the carbon chain length of such group may be extended to 20 carbon atoms) onto which an aryl or heterocyclic radical (such as defined above) is already bonded, and wherein the said aliphatic radical and/or the said aryl or heterocyclic radical may be optionally substituted with one or more substituents independently selected from the group consisting of halogen, amino, hydroxyl, sulfhydryl, C 1-7 alkyl, trifluoromethyl and nitro, such as but not limited to benzyl, 4- chlorobenzyl, 4-fluorobenzyl, 2-fluorobenzyl, 3,4-dichlorobenzyl, 2,6-dichlorobenzyl, 3- methylbenzyl, 4-methylbenzyl, 4-fer-butylbenzyl, phenylpropyl, 1-naphthylmethyl, phenylethyl, 1- amino-2-phenylethyl, 1-amino-2-[4-hydroxyphenyl]ethyl, 1-
  • heteroaryl refers respectively to an aryl, heteroaryl, cycloalkyl or heterocyclic radical (such as defined above) onto which are already bonded one or more aliphatic saturated or unsaturated hydrocarbon monovalent radicals, preferably one or more C ⁇ -7 alkyl, C 2 .
  • alkenyl or C 3- ⁇ 0 cycloalkyl radicals as defined above such as, but not limited to, o-toluyl, m-toluyl, p-toluyl, 2,3-xylyl, 2,4-xylyl, 3,4-xylyl, o-cumenyl, m-cumenyl, p- cumenyl, o-cymenyl, m-cymenyl, p-cymenyl, mesityl, fer-butylphenyl, lutidinyl (i.e.
  • alkoxyaryl refers to an aryl radical (such as defined above) onto which is (are) bonded one or more C ⁇ -7 alkoxy radicals as defined above, preferably one or more methoxy radicals, such as, but not limited to, 2-methoxy phenyl, 3-methoxyphenyl, 4-methoxy phenyl, 3,4-dimethoxyphenyl, 2,4,6- trimethoxyphenyl, methoxynaphtyl and the like.
  • alkylamino means that respectively one (thus monosubstituted amino) or even two (thus disubstituted amino) C - alkyl, C 3 _ 0 cycloalkyl, C 2 .
  • alkynyl radical(s) (each of them as defined herein, respectively) is/are attached to a nitrogen atom through a single bond, such as but not limited to, anilino, benzylamino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, propenylamino, n-butylamino, ter-butylamino, dibutylamino, morpholinoalkylamino, 4-morpholinoanilino, hydroxymethylamino, ⁇ - hydroxyethylamino and ethynylamino; this definition also includes mixed disubstituted amino radicals wherein the nitrogen atom is attached to two such radicals belonging to two different subset of radicals, e.g.
  • an alkyl radical and an alkenyl radical or to two different radicals within the same sub-set of radicals, e.g. methylethylamino; among disubstituted amino radicals, symetricaliy substituted are usually preferred and more easily accessible.
  • the terms "(thio)carboxy!ic acid (thio)ester " and “ (thio)carboxylic acid (thio)amide " refer to substituents wherein the carboxyl or thiocarboxyl group is bonded to the hydrocarbonyl residue of an alcohol, a thiol, a polyol, a phenol, a thiophenol, a primary or secondary amine, a polyamine, an amino-alcohol or ammonia, the said hydrocarbonyl residue being selected from the group consisting of C ⁇ -7 alkyl, C 2- alkenyl, C 2-7 alkynyl, C 3 .
  • cycloalkyl C 3 _ 10 cycloalkenyl, aryl, arylalkyl, alkylaryl, alkylamino, cycloalkylamino, alkenylamino, cycloalkenylamino, arylamino, arylalkylamino, heterocyclic amino, heterocyclic-substituted alkylamino, heterocyclic-substituted arylamino, hydroxyalkylamino, mercapto-alkylamino or alkynylamino (each such as above defined, respectively).
  • alkylammonium and arylammonium mean a tetra-coordinated nitrogen atom being linked to one or more C ⁇ - alkyl, C 3 _ 0 cycloalkyl, aryl or heteroaryl groups, each such as above defined, respectively.
  • the term "Schiff base" conventionally refers to the presence of an imino group (usually resulting from the reaction of a primary amine with an aldehyde or a ketone) in the said ligand, preferably being part of a multidentate ligand (such as defined in http://www.ilpi.com/organomet/coordnum.html) which may be coordinated to the metal, in addition to the nitrogen atom of said imino group, through at least one further heteroatom selected from the group consisting of oxygen, sulfur, selenium, nitrogen, phosphorus, arsenic and antimony.
  • the said multidentate ligand may be for instance, but without limitation, selected from the group consisting of: a N.O-bidentate Schiff base ligand such as a lumazine or substituted lumazine or 2-(2- hydroxyphenyl)benzoxazole or (2'-hydroxyphenyl)-2-thiazoline; a N,S-bidentate Schiff base ligand such as a thiolumazine or substituted thiolumazine; a N,N-bidentate or N.O-bidentate or N,S-bidentate ligand being a salicylaldimine such as the reaction product of an optionally substituted salicylaldehyde (such as, but not limited to, tert- butyl-salicylaldehyde, 6-phenyl-salicylaldehyde, 2-(9-phenanthrene) salicylaldehyde, 2-(9- anthracene) salicylalde
  • R 2 may be selected from the group consisting of hydrogen, halogen, nitro, C ⁇ -7 alkyl, aryl and arylalkyl
  • R 3 may be hydrogen or aryl
  • R 4 may be selected from the group consisting of hydrogen, C 1-7 alkyl and aryl
  • R 5 may be selected from the group consisting of hydrogen, aryl and alkylaryl), or ⁇ -(2- methoxyphenyl) salicylideneamine, or salicylaldehyde-2-hydroxanil, or the heterocyclic Schiff base resulting from the reaction of 1-amino-5-benzoyl-4-phenyl-1 H pyrimidin-2-one with 2- hydroxynaphtaldehyde, or the thenoyltrifluoroaceto antipyrine Schiff base resulting from the reaction of thenoyl-trifluoroacetone with 4-aminoantipyrine; a 0,N,
  • Schiff base as used herein also refers to Schiff base ligands with thioether or coumarin groups.
  • the multidentate ligand may include more than one Schiff base, for instance as shown in figures 2 and 3, thus possibly resulting in 0,N,N,0-tetradentate or 0,N,N,N- tetradentate or N,N,N,N-tetradentate Schiff base ligands.
  • constraint steric hindrance relates to a group or ligand, usually a branched or substituted group or ligand, which is constrained in its movements, i.e.
  • stereoisomer refers to all possible different isomeric as well as conformational forms which the compounds of the invention may possess, in particular all possible stereochemically and conformationally isomeric forms, all diastereomers, enantiomers and/or conformers of the basic molecular structure. Some compounds of the present invention may exist in different tautomeric forms, all of the latter being included within the scope of the present invention.
  • enantiomer means each individual optically active form of a compound of the invention, having an optical purity or enantiomeric excess (as determined by methods standard in the art) of at least 80% (i.e. at least 90% of one enantiomer and at most 10% of the other enantiomer), preferably at least 90% and more preferably at least 98%.
  • solvate includes any combination which may be formed by a compound of this invention with a suitable inorganic solvent (e.g.
  • organic solvent such as but not limited to alcohols (in particular ethanol and isopropanol), ketones (in particular methylethylketone and methylisobutylketone), esters (in particular ethyl acetate) and the like.
  • the present invention relates to an at least tetra-coordinated metal complex, a salt, a solvate or an enantiomer thereo , comprising: - a multidentate ligand being coordinated with the metal by means of a nitrogen atom and at least one heteroatom selected from the group consisting of oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic and antimony, wherein each of nitrogen, phosphorus, arsenic and antimony is substituted with a radical R"" selected from the group consisting of hydrogen, C ⁇ _ 7 alkyl, C 3 .
  • cycloalkenyl groups the said aromatic or unsaturated cycloaliphatic group being optionally substituted with one or more C 1-7 alkyl groups or with electron-withdrawing groups such as, but not limited to, halogen, nitro, cyano, (thio)carboxylic acid, (thio)carboxylic acid (thio)ester, (thio)carboxylic acid (thio)amide, (thio)carboxylic acid anhydride and (thio) carboxylic acid halide; and a non-anionic ligand L 2 selected from the group consisting of C 1-7 alkyl, C 3- ⁇ D cycloalkyl, aryl, arylalkyl, alkylaryl and heterocyclic, the said group being optionally substituted with one or more preferably electron-withdrawing substituents such as, but not limited to, halogen, nitro, cyano, (thio)carboxylic acid, (thio)carboxylic acid (thio)
  • the multidentate ligand is preferably a multidentate Schiff base such as above defined, more preferably a N.O-bidentate Schiff base ligand or N,S- bidentate Schiff base ligand, most preferably a bidentate Schiff base ligand as shown in formulae (IA) or (IB) in figure 1 and described in more detail hereinafter, or as shown in the above described formulae (V) or (VI) in figure 6, in which case the metal complex is tetra-coordinated.
  • the multidentate ligand may also be a tridentate Schiff base, in which case the metal complex is penta- coordinated.
  • the at least tetra-coordinated metal complex according to this first aspect of the invention preferably is a monometallic complex.
  • the metal is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table. More preferably the said metal is selected from the group consisting of indium, ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt.
  • each of the metal, the radical R"", the ligand L 1 and the ligand L 2 may, independently from each other, be any of the above-mentioned metals or any of the above-mentioned groups with any of the substituents listed for such groups, including any of the individual meanings for such groups or substituents which are listed in the definitions given hereinabove.
  • the non-anionic ligand L 2 has constraint steric hindrance such as, but not limited to, tert-butyl, neopentyl and mono- or polysubstituted phenyl, e.g. pentafluorophenyl.
  • L 2 may also be a linear C ⁇ _ 7 alkyl such as methyl, or phenyl.
  • the substituting radical R"" also has constraint steric hindrance such as, but not limited to, tert-butyl, neopentyl and mono- or polysubstituted phenyl, e.g. 2,6- diisopropylphenyl, 2,6-ditert-butylphenyl or 2,6-diisopropyl-4-bromophenyl.
  • the non- anionic unsaturated ligand L 1 also has constraint steric hindrance (such as, but not limited to, alkylaryl and alkylheteroaryl, e.g.
  • the at least tetra-coordinated metal complex according to this first aspect of the invention may for instance, but without limitation, be made according to the following procedure: a metal (e.g. thallium) salt of the multidentate ligand (e.g.
  • the bidentate or tridentate Schiff base is first reacted with a preferably bimetallic metal complex of the desired metal, more preferably a homobimetallic complex wherein the desired metal is coordinated with a non-anionic unsaturated ligand L 1 and at least one anionic ligand, such as [RuCI 2 (p-cymene)] 2 , [RuCI 2 (COD)] 2 or [RuCl 2 (NBD)] 2 , wherein COD and NBD respectively mean cyclooctadiene and norbornadiene.
  • the intermediate complex i.e.
  • a non-anionic unsaturated ligand L 1 the multidentate ligand (e.g. the bidentate or tridentate Schiff base) and an anionic ligand
  • an alcali or alcaline-earth metal e.g. a C _ 7 alkyllithium, a C 1-7 al
  • Recovery of the desired at least tetra-coordinated metal complex of the invention is achieved by removal of the alcali or alcaline-earth metal salt formed with the anionic ligand, followed by purification using conventional techniques. High yields of the pure at least tetra-coordinated metal complex of the invention may thus be achieved in a simple two-steps method.
  • the present invention relates to a hexa-coordinated metal complex, a salt, a solvate or an enantiomer thereof, comprising: - a multidentate ligand being coordinated with the metal by means of a nitrogen atom and at least one heteroatom selected from the group consisting of oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic and antimony, wherein each of nitrogen, phosphorus, arsenic and antimony is substituted with a radical R"" selected from the group consisting of hydrogen, C -7 alkyl, C 3 .
  • Said hexa-coordinated metal complex is preferably a bimetallic complex wherein each metal is hexa-coordinated.
  • the two metals may be the same or different.
  • each metal is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the
  • each said metal is selected from the group consisting of iridium, ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt.
  • the multidentate ligand is preferably defined as in the first aspect of the invention, i.e. preferably is a bidentate or tridentate Schiff base.
  • the substituting radical R"" has constraint steric hindrance such as, but not limited to, tert-butyl, neopentyl and mono- or polysubstituted phenyl, e.g. 2,6-diisopropylphenyl, 2,6-ditert-butylphenyl or 2,6-diisopropyl-4- bromophenyl.
  • the non-anionic bidentate ligand L 3 is preferably a polyunsaturated C 3 .
  • cycloalkenyl group such as, but not limited to, norbornadiene, cyclooctadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene or cycloheptatriene, or a heteroaryl group such as defined hereinabove, for instance (but without limitation) a 1-hetero-2,4-cyclopentadiene such as pyrrole, furan or thiophene, or a fused-ring derivative thereof such as indole, or a six-membered heteroaromatic compound such as pyridine, pyridazine, pyrimidine, pyrazine, triazines or tetrazines, or a fused-ring derivative thereof such as quinoline, isoquinoline, cinnoline, phtalazine, quinazoline, quinoxaline, pyridopyrimidine or pteridine.
  • Each anionic ligand L 4 is preferably selected from the group consisting of C 1-2 o carboxylate, C ⁇ -20 alkoxy, C 2 . 2 o alkenyloxy, C 2-2 o alkynyloxy, aryloxy, C 1-20 alkoxycarbonyl, C ⁇ -7 alkylthio, C ⁇ . 20 alkylsulfonyl, C 1-20 alkylsulfinyl C -2 o alkylsulfonate, arylsulfonate, C 1-20 aikylphosphonate, arylphosphonate, C ⁇ - 20 alkylammonium, arylammonium, alkyldiketonate (e.g.
  • hexa-coordinated metal complex is monometallic, it preferably has only one anionic ligand L 4 .
  • the hexa-coordinated metal complex according to this second aspect of the invention may for instance, but without limitation, be made in high yield and purity in a one-step procedure, wherein a metal (e.g. thallium) salt of the multidentate ligand (e.g.
  • the bidentate or tridentate Schiff base is reacted with a preferably bimetallic metal complex of the desired metal, more preferably a homobimetallic complex wherein the desired metal is coordinated with a non-anionic bidentate ligand L 3 and at least one anionic ligand, such as [RuCI 2 L 3 ] 2 , e.g. [RuCI 2 (COD)] 2 or [RuCI 2 (NBD)] 2 , wherein COD and NBD respectively mean cyclooctadiene and norbornadiene.
  • the desired hexa-coordinated metal complex may be purified using conventional techniques.
  • anionic ligands L 4 of said hexa-coordinated metal complex is (are) abstracted and replaced with a solvent S as a ligand.
  • This anionic ligand abstraction and replacement may be effected for instance by treating, in the presence of the solvent S, the hexa-coordinated metal complex of this second aspect of the invention with an equivalent amount of a compound having the formula A-E, wherein
  • L 4 E is a trimethylsilyl group or a metal such as silver, thus resulting in a modified hexa-coordinated metal complex being a cationic species having the solvent S as a ligand (in place of L 4 ) and being associated with an anion A.
  • the treatment also results in the formation of a compound L 4 E (e.g. silver chloride or chlorotrimethyisilane) which can be removed from the reaction mixture by conventional techniques.
  • Suitable anions A for this purpose may be, but without limitation, selected from the group consisting of hexafluorophosphate, hexafluoroantimoniate, hexafluoroarseniate, perchlorate, tetrafluoroborate, tetra(pentafluorophenyl)borate, alkylsulfonates wherein the alkyl group may be substituted with one or more halogen atoms, and arylsulfonates (e.g. toluenesulfonate).
  • Suitable solvents S for coordinating with the metal in such a cationic species may be selected from the group consisting of protic solvents, polar aprotic solvents and non-polar solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides, and water.
  • both the at least tetra-coordinated metal complex of the first aspect of the invention and the hexa-coordinated metal complex of the second aspect of the invention may have, as a multidentate ligand, a bidentate Schiff base having the above described formulae (V) or (VI) shown in figure 6, or one of the general formulae (IA) or (IB) referred to in figure 1 , wherein: - Z is selected from the group consisting of oxygen, sulphur, selenium, NR"", PR"", AsR"" and SbR"", wherein R"" is a radical selected from the group consisting of hydrogen, C 1-7 alkyl, C 3-10 cycloalkyl, aryl and heteroaryl; R" and R"' are each a radical independently selected from the group consisting of hydrogen, C 1-6 alkyl, C 3 .
  • R" and R'" together form a phenyl group which may be substituted with one or more preferably branched alkyl groups such as isopropyl or tert-butyl.
  • the substituting radical R"" has constraint steric hindrance such as, but not limited to, tert-butyl, neopentyl and mono- or polysubstituted phenyl, e.g. 2,6-diisopropylphenyl, 2,6-ditert- butylphenyl or 2,6-diisopropyl-4-bromophenyl.
  • the class of bidentate Schiff bases having the general formula (IA) is well known in the art arid may be made for instance by condensing a salicylaldehyde with a suitably substituted aniline.
  • the class of bidentate Schiff bases having the general formula (IB) may be made for instance by condensing benzaldehyde with a suitably selected amino-alcohol such as o-hydroxyaniline (when Z is oxygen), an amino-thiol (when Z is sulphur), a diamine, (when Z is NR"”), an aminophosphine (when Z is PR"”), an aminoarsine
  • this invention also provides a process for the radical polymerisation of a monomer in the presence, as a catalyst component, of a tetra-coordinated metal complex, a salt, a solvate or an enantiomer thereof, comprising: two anionic ligands L 8 ; a non-anionic unsaturated ligand L 9 selected from the group consisting of aromatic and unsaturated cycloaliphatic groups, preferably aryl, heteroaryl and C 4-20 cycloalkenyl groups, the said aromatic or unsaturated cycloaliphatic group being optionally substituted with one or more C ⁇ -7 alkyl groups or with electron-withdrawing groups such as, but not limited to, halogen, nitro, cyano, (thio)carboxylic acid, (thio)carboxylic acid (thio)ester, (thio)carboxylic acid (thio)
  • each anionic ligand L 8 is preferably selected from the group consisting of C 1-20 carboxylate, C 1-20 alkoxy, C 2-2 o alkenyloxy, C 2-2 o alkynyloxy, aryloxy, C ⁇ -20 alkoxycarbonyl, C 1-7 alkylthio, C ⁇ _ 20 alkylsulfonyl, C ⁇ . 20 alkylsulfinyl C ⁇ -20 alkylsulfonate, arylsulfonate, C 1-2 o aikylphosphonate, arylphosphonate, alkyldiketonate (e.g. acetyl-acetonate), aryldiketonate, halogen, nitro and cyano, each of the said groups being as defined hereinabove.
  • the non-anionic unsaturated ligand L 9 has constraint steric hindrance (such as, but not limited to, alkylaryl and alkylheteroaryl, e.g. xylyl, cumenyl or mesityl).
  • the monoamine ligand L 10 may include one (primary amine), two (secondary amine) or even three (tertiary amine) saturated aliphatic groups such as C ⁇ -7 alkyl or C 3 _ ⁇ o cycloalkyl (each of them as defined hereinabove, respectively) being attached to the nitrogen atom through a single bond or, in the case of aliphatic secondary amines, may be a saturated heterocyclic monoamine.
  • the ligand L 10 may be represented by the general formula NR R 8 R ⁇ 9 wherein each of R ⁇ 7> R 18 and R 19 is independently selected from the group consisting of hydrogen, C 1-7 alkyl and C 3-10 cycloalkyl, provided that at most two of R 17 , R 18 and R 9 are hydrogen, or two of them may together form a saturated heterocyclic group preferably having from 5 to 7 carbon atoms.
  • Illustrative examples include, but are not limited to, methylamine, dimethylamine, ethylamine, diethylamine, isopropylamine, diisopropylamine, n-butylamine, isobutylamine, ter-butylamine, dibutylamine, cyclopentyl-amine, dicyclopentylamine, cyclohexylamine, dicyclohexylamine, triethylamine, triisopropylamine, tri-butylamine, methylethylamine, norbomylamine, adamantylamine, piperidine, 1-ethylpiperidine and 1 ,4-diazabicyclo-[2.2.2]octane.
  • Suitable diamines include N,N'-dimethyl- ethylenediamine and N,N,N',N'-tetramethylethylenediamine.
  • the tetra-coordinated metal complex used is preferably a monometallic complex wherein the metal is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table.
  • the said metal is selected from the group consisting of iridium, ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt.
  • each of the metal, the anionic ligands L 8 , the non- anionic ligand L 9 and the ligand L 10 may, independently from each other, be any of the above- mentioned metals or any of the above-mentioned groups with any of the substituents listed for such groups, including any of the individual meanings for such groups or substituents which are listed in the definitions given hereinabove.
  • the tetra-coordinated metal complex used within this third aspect of the invention may be prepared, by similarity with a procedure described by Carter et al.
  • the radical polymerisation process of this third aspect of the invention is a living atom transfer radical polymerisation which is operated under the conditions (including concentration of growing radicals, initiator, solvent, temperature and the like) and is applicable to the monomers indicated below with respect to the sixth aspect of the invention.
  • this radical polymerisation process proceeds at an enhanced rate when compared to the polymerisation of the same monomer under the same conditions in the combined presence of a chlorotriphenylphosphino ruthenium complex and of a primary, secondary, cyclic secondary or tertiary amine additive, as described by Hamasaki et al. in Macromolec ⁇ les (2002) 35:2934-2940.
  • the present invention provides a catalytic system comprising: (a) as the main catalytic species, the hexa-coordinated metal complex of the second aspect of the invention (including the modified cationic species thereof having a solvent S as a ligand), or the tetra-coordinated metal complex used in the third aspect of the invention, or an at least tetra- coordinated metal complex, a salt, a solvate or an enantiomer thereof, comprising: a multidentate ligand being coordinated with the metal by means of a nitrogen atom and at least one heteroatom selected from the group consisting of oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic and antimony, wherein each of nitrogen, phosphorus, arsenic and antimony is substituted with a radical R"" selected from the group consisting of hydrogen, C ⁇ -7 alkyl, C 3- ⁇ 0 cycloalkyl, aryl and heteroaryl; a non-anionic uns
  • one or more second catalyst components being selected from the group consisting of Lewis acid co-catalysts (bi), catalyst activators (b 2 ) and initiators having a radically transferable atom or group (b 3 ).
  • the latter alternative of the main catalytic species includes the metal complex of the first aspect of the invention (when L 6 is a non-anionic ligand), but is not limited thereto since the ligand
  • L 6 may also be an anionic ligand preferably selected from the group consisting of C 1-20 carboxylate,
  • acetylacetonate namely when the complex is to be used in the presence of water, it may be advantageous when the anionic ligand L 6 is abstracted and replaced with a solvent S as a ligand.
  • This anionic ligand abstraction and replacement may be effected for instance by treating, in the presence of the solvent S, the at least tetra-coordinated metal complex having the anionic ligand L 6 with an equivalent amount of a compound having the formula A-E, wherein E is a trimethylsilyl group or a metal such as silver, thus resulting in a modified at least tetra-coordinated metal complex being a cationic species having the solvent S as a ligand (in place of L 6 ) and being associated with an anion A.
  • the treatment also results in the formation of a compound L 6 E (e.g. silver chloride or chlorotrimethylsilane) which can be removed from the reaction mixture by conventional techniques.
  • a compound L 6 E e.g. silver chloride or chlorotrimethylsilane
  • Suitable anions A for this purpose may, but without limitation, be selected from the group consisting of hexafluorophosphate, hexafluoroantimoniate, hexafluoroarseniate, perchlorate, tetrafluoroborate, tetra(pentafluoro-phenyl)borate, alkylsulfonates wherein the alkyl group may be substituted with one or more halogen atoms, and arylsulfonates (e.g. toluenesulfonate).
  • Suitable solvents S for coordinating with the metal in such a cationic species may be selected from the group consisting of protic solvents, polar aprotic solvents and non-polar solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides, and water.
  • L 6 is a non-anionic ligand, it preferably has constraint steric hindrance such as, but not limited to, tert-butyl, neopentyl and mono- or polysubstituted phenyl, e.g. pentafluorophenyl.
  • L 6 may also be methyl or phenyl.
  • the substituting radical R"" also has constraint steric hindrance such as, but not limited to, tert-butyl, neopentyl and mono- or polysubstituted phenyl, e.g. 2,6-diisopropylphenyl, 2,6-ditert-butylphenyl or 2,6-diisopropyl-4-bromophenyl.
  • the non-anionic unsaturated ligand L 5 also has constraint steric hindrance (such as, but not limited to, alkylaryl and alkylheteroaryl, e.g. xylyl, cumenyl or mesityl.
  • the second component (b) will be selected according to the kind of reaction to be catalyzed.
  • a co-catalyst (b) may be useful for increasing the reaction rate of the ring opening metathesis polymerisation of cyclic olefins and may be selected, but without limitation, from the group consisting of boron trihalides; trialkylboron; triarylboron; organoaluminum compounds; magnesium halides; aluminum halides; titanium or vanadium trihalides or tetrahalides or tetraalkoxides, preferably titanium tetrachloride or tetraisopropoxytitanium; antimony and bismuth pentahalides.
  • a co-catalyst may be an organoaluminum compound selected from the group consisting of tri-n-alkylaluminums; dialkylaluminum hydrides, trialkenylaluminums, alkylaluminum alkoxides, dialkylaluminum alkoxides, dialkylaluminum aryloxides and dialkyl-aluminum halides.
  • a catalyst activator (b 2 ) may also be useful for increasing the reaction rate of the ring opening metathesis polymerisation of cyclic olefins (thus may be combined with a co-catalyst (b ) such as above defined) and may be a diazo compound such as, but not limited to, ethyldiazoacetate and trimethylsilyldiazomethane.
  • a co-catalyst such as above defined
  • an initiator having a radically transferable atom or group (b 3 ) is usually required, together with the main catalytic species, for performing the radical polymerisation of a monomer since an ATRP catalytic system is based on the reversible formation of growing radicals in a redox reaction between the metal component and an initiator.
  • Suitable initiators include those compounds having the general formula R 35 R 36 R 37 CX wherein: X ! is selected from the group consisting of halogen, OR 38 (wherein R 38 is selected from C ⁇ _ 20 alkyl, polyhaloC ⁇ -20 alkyl, C 2 .
  • alkynyl preferably acetylenyl
  • C 2-2 o alkenyl preferably vinyl
  • phenyl optionally substituted with 1 to 5 halogen atoms or C 1- alkyl groups and phenyl-substituted C 1-7 alkyl
  • R 39 is aryl or C ⁇ -20 alkyl, or where an N(R 39 ) 2 group is present, the two R 39 groups may be joined to form a 5-, 6- or 7-membered heterocyclic ring (in accordance with the definition of heteroaryl above), and R 35, R 36 and R 37 are each independently selected from the group consisting of hydrogen, halogen, C -20 alkyl (preferably C
  • X ! is preferably bromine, which provides both a higher reaction rate and a lower polymer polydispersity.
  • X ! is preferably bromine, which provides both a higher reaction rate and a lower polymer polydispersity.
  • the alkyl group may be further substituted with an X group as defined above.
  • the initiator it is possible for the initiator to serve as a starting molecule for branch or star (co)polymers.
  • One example of such an initiator is a 2,2-bis(halomethyl)-1 ,3-dihalopropane (e.g.
  • R 3 is phenyl substituted with from one to five C 1-6 alkyl substituents, each of which may independently be further substituted with a X 1 group (e.g. , ⁇ '-dibromoxylene, hexakis( ⁇ -chloro- or -bromomethyl)benzene).
  • a X 1 group e.g. , ⁇ '-dibromoxylene, hexakis( ⁇ -chloro- or -bromomethyl)benzene.
  • Preferred initiators include 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile and C 1-7 alkyl esters of a 2-halo-C 1-7 carboxylic acid (such as 2-chloropropionic acid, 2-bromopropionic acid, 2- chloroisobutyric acid, 2-bromo-isobutyric acid and the like).
  • Another example of a suitable initiator is dimethyl-2-chloro-2,4,4-trimethylglutarate.
  • the present invention also provides a supported catalyst, preferably for use in a heterogeneous catalytic reaction, comprising: (a) a catalytically active metal complex being selected from the group consisting of the at least tetra-coordinated metal complexes of the first aspect of the invention, the hexa-coordinated metal complexes of the second aspect of the invention (including the modified cationic species thereof having a solvent S as a ligand and being associated with an anion A), or the tetra-coordinated metal complexes used in the third aspect of the invention, or a catalytic system according to the fourth aspect of the invention, and (b) a supporting amount of a carrier suitable for supporting said catalytically active metal complex or catalytic system (a).
  • a catalytically active metal complex being selected from the group consisting of the at least tetra-coordinated metal complexes of the first aspect of the invention, the hexa-coordinated metal complexes of the second aspect of the invention (
  • said carrier may be selected from the group consisting of porous inorganic solids (including silica, zirconia and alumino-silica), such as amorphous or paracrystalline materials, crystalline molecular sieves and modified layered materials including one or more inorganic oxides, and organic polymer resins such as polystyrene resins and derivatives thereof.
  • Porous inorganic solids that may be used with the catalysts of the invention have an open microstructure that allows molecules access to the relatively large surface areas of these materials that enhance their catalytic and sorptive activity. These porous materials can be sorted into three broad categories using the details of their microstructure as a basis for classification.
  • Amorphous and paracrystalline supports These categories are the amorphous and paracrystalline supports, the crystalline molecular sieves and modified layered materials.
  • the detailed differences in the microstructures of these materials manifest themselves as important differences in the catalytic and sorptive behavior of the materials, as well as in differences in various observable properties used to characterize them, such as their surface area, the sizes of pores and the variability in those sizes, the presence or absence of X-ray diffraction patterns and the details in such patterns, and the appearance of the materials when their microstructure is studied by transmission electron microscopy and electron diffraction methods.
  • Amorphous and paracrystalline materials represent an important class of porous inorganic solids that have been used for many years in industrial applications.
  • Typical examples of these materials are the amorphous silicas commonly used in catalyst formulations and the paracrystalline transitional aluminas used as solid acid catalysts and petroleum reforming catalyst supports.
  • amorphous is used here to indicate a material with no long range order and can be somewhat misleading, since almost all materials are ordered to some degree, at least on the local scale.
  • An alternate term that has been used to describe these materials is "X-ray indifferent".
  • the microstructure of the silicas consists of 100-250 Angstrom particles of dense amorphous silica (Kirk-Othmer Encyclopedia of Chemical Technology, 3rd. ed., vol. 20, 766-781 (1982)), with the porosity resulting from voids between the particles.
  • Paracrystalline materials such as the transitional aluminas also have a wide distribution of pore sizes, but better defined X-ray diffraction patterns usually consisting of a few broad peaks.
  • the microstructure of these materials consists of tiny crystalline regions of condensed alumina phases and the porosity of the materials results from irregular voids between these regions (K. Wefers and Chanakya Misra, "Oxides and Hydroxides of Aluminum", Technical Paper No 19 Revised, Alcoa Research Laboratories, 54-59 (1987)). Since, in the case of either material, there is no long range order controlling the sizes of pores in the material, the variability in pore size is typically quite high. The sizes of pores in these materials fall into a regime called the mesoporous range,, including, for example, pores within the range of about 15 to about 200 Angstroms.
  • zeolites In sharp contrast to these structurally ill-defined solids are materials whose pore size distribution is very narrow because it is controlled by the precisely repeating crystalline nature of the materials' microstructure. These materials are called “ molecular sieves " the most important examples of which are zeolites. Zeolites, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material.
  • molecular sieves Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials are known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties. Such molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline silicates.
  • silicates can be described as a rigid three-dimensional framework of Si04 and Periodic Table Group IIIB element oxide, e.g., AI04, in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total Group IIIB element, e.g., aluminum, and Group IVB element, e.g., silicon, atoms to oxygen atoms is 1 :2.
  • the electrovalence of the tetrahedra containing the Group IIIB element, e.g., aluminum is balanced by the inclusion in the crystal of a cation, for example, an alkali metal or an alkaline earth metal cation.
  • a molecular sieve composition SSZ-25 is taught in U.S. Pat. No. 4,826,667 and European Patent Application 231 ,860, said zeolite being synthesized from a reaction mixture containing an adamantane quaternary ammonium ion.
  • Molecular sieve material being selected from the group consisting of zeolites REY, USY, REUSY, dealuminated Y, ultrahydrophobic Y, silicon-enriched dealuminated Y, ZSM-20, Beta, L, silicoaluminophosphat.es SAPO-5, SAPO-37, SAPO-40, MCM-9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5 and mesoporous crystalline MCM-41 are suitable for including into a supported catalyst of this invention.
  • MCM-41 has a uniform structure exhibiting hexagonal arrangement of straight mesopores, such as honeycomb, and has a specific surface area of about 1 ,000 m 2 /g as measured by ordinary BET.
  • Mesoporous molecular sieves have regularly arranged channels larger than those of existing zeolites, thus enabling their application to adsorption, isolation or catalyst conversion reactions of relatively large molecules; a family of high quality, hydrothermally stable and ultra large pore size mesoporous silicas by using amphiphilic block copolymers in acidic media as disclosed by U.S. Patent No. 6,592,764.
  • One member of the family, SBA-15 has a highly ordered, two-dimensional hexagonal honeycomb, hexagonal cage or cubic cage mesostructure.
  • 6,630,170 discloses a mesoporous composition prepared from a mixture comprising hydrochloric acid, vitamin E and a silica source, wherein said vitamin E functions as a templating molecule, and said mesoporous composition exhibits uniform pore size; and - U.S. Patent No. 6,669,924 discloses a mesoporous zeolitic material having a stereoregular arrangement of uniformly-sized mesopores with diameters ranging from 2 to 50 nm and walls having a thickness of at least 4 nm and a microporous nanocrystalline structure, the mesopore walls having a stereoregular arrangement of uniformly-sized micropores with diameters less than 1.5 nm.
  • Certain layered materials which contain layers capable of being spaced apart with a swelling agent, may be pillared to provide materials having a large degree of porosity.
  • Examples of such layered materials include clays. Such clays may be swollen with water, whereby the layers of the clay are spaced apart by water molecules.
  • Other layered materials are not swellable with water, but may be swollen with certain organic swelling agents such as amines and quaternary ammonium compounds. Examples of such non-water swellable layered materials are described in U.S. Pat. No. 4,859,648 and include layered silicates, magadiite, kenyaite, trititanates and perovskites.
  • non-water swellable layered material which can be swollen with certain organic swelling agents, is a vacancy-containing titanometallate material, as described in U.S. Pat. No. 4,831 ,006.
  • a layered material Once a layered material is swollen, the material may be pillared by interposing a thermally stable substance, such as silica, between the spaced apart layers.
  • a thermally stable substance such as silica
  • the present invention provides the use of a hexa-coordinated metal complex according to the second aspect of the invention (including the modified cationic species thereof having a solvent S as a ligand and being associated with an anion A) or an at least tetra- coordinated metal complex, a salt, a solvate or an enantiomer thereof, comprising: a multidentate ligand being coordinated with the metal by means of a nitrogen atom and at least one heteroatom selected from the group consisting of oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic and antimony, wherein each of nitrogen, phosphorus, arsenic and antimony is substituted with a radical R"" selected from the group consisting of hydrogen, C 1-7 alkyl, C 3 .
  • a multidentate ligand being coordinated with the metal by means of a nitrogen atom and at least one heteroatom selected from the group consisting of oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic and
  • a non-anionic unsaturated ligand L 5 selected from the group consisting of aromatic and unsaturated cycloaliphatic groups, preferably aryl, heteroaryl and C 4-2 o cycloalkenyl groups, the said aromatic or unsaturated cycloaliphatic group being optionally substituted with one or more C -6 alkyl groups or electron-withdrawing groups such as, but not limited to, halogen, nitro, cyano, (thio)carboxylic acid, (thio)carboxylic acid (thio)ester, (thio)carboxylic acid (thio)amide, (thio)carboxylic acid anhydride and (thio) carboxylic acid halide; and - a ligand L 6 being either an anionic ligand or a non-anionic ligand selected from the group consisting of C -7 alkyl, C 3 .
  • acetylene metathesis may be referred to herein as a reaction in which all carbon-carbon triple bonds in a mixture of alkynes are cut and then rearranged in a statistical fashion.
  • An atom or group transfer reaction usually comprises the step of reacting the said ethylenically or acetylenically unsaturated compound or other reactive substrate with a second reactive substrate under suitable reaction conditions and in the presence of a suitable catalytic component, the second reactive substrate being a suitable donor for the atom or group to be transferred.
  • the catalytic component is such as above defined, i.e. namely includes the metal complexes of both the first and second aspects of the invention but is not limited thereto.
  • the said atom or group transfer reactions may be, but without limitation, selected from the group consisting of: atom or group transfer radical polymerisation of one or more radically (co)polymerisable monomers, especially mono- and diethylenically unsaturated monomers; atom transfer radical addition (the latter being as explained in the background of the invention), e.g. the addition of a polyhalomethane having the formula CX n H .
  • X is halogen and n is an integer from 2 to 4, onto an ethylenically unsaturated compound to produce the corresponding saturated polyhalogenated adduct, including for instance the addition of carbon tetrachloride or chloroform onto an ⁇ -olefin; vinylation reaction, i.e. the reaction of a mono- or di-alkyne (e.g. phenylacetylene or 1 ,7- octadiyne) with a monocarboxylic acid (e.g.
  • saturated hydrocarbons such as, but not limited to, methane
  • phosphines for producing phosphonates, or alcohols and aldehydes for producing carboxylic acids; cyclopropenation of an alkyne for producing an organic compound having one or more cyclopropene structural units; - hydrocyanation of ⁇ -ethylenically unsaturated compounds for producing saturated nitriles, or alkynes for producing unsaturated nitriles, or ⁇ , ⁇ -unsaturated aldehydes or ketones for producing ⁇ -cyano carbonyl compounds; hydrosilylation of olefins for producing saturated silanes, or alkynes for producing unsaturated silanes, or ketones for producing silyl ethers, or trimethylsilylcyanation of aldehydes for producing cyanohydrin trimethylsilyl ethers; aziridination of imines or alkenes for producing organic compounds having one or more aziridine structural units; hydroamidation of olefins for producing saturated amides; hydrogenation of o
  • Each of the above organic synthesis reactions which will be described in more detail hereinafter, is known per se.
  • Each organic synthesis reaction of this sixth aspect of the invention may be conducted in a continuous, semi-continuous, or batch manner and may involve a liquid and/or gas recycling operation as desired.
  • the manner or order of addition of the reactants, catalyst, and solvent are usually not critical.
  • each organic synthesis reactions may be carried out in a liquid reaction medium that contains a solvent for the active catalyst, preferably one in which the reactants, including catalyst, are substantially soluble at the reaction temperature.
  • the said reaction is an olefin metathesis reaction for transforming a first olefin into at least one second olefin or into a linear olefin oligomer or polymer or into a cyclo-olefin.
  • the invention thus relates to a method for performing an olefin metathesis reaction comprising contacting at least one first olefin with the catalytic component, optionally supported on a suitable carrier such as decribed hereinabove with reference to the fifth aspect of the invention.
  • olefin metathesis reactions enabled by the metal complexes of the present invention include, but are not limited to, RCM of acyclic dienes, cross metathesis reactions, de-polymerization of olefinic polymers and, more preferaby, ROMP of strained cyclic olefins.
  • the catalytic components of this invention may catalyze ROMP of unsubstituted, monosubstituted and disubstituted strained mono-, bi- and polycyclic olefins with a ring size of at least 3, preferably 3 to 5, atoms; examples thereof include norbornene, cyclobutene, norbornadiene, cyclopentene, dicyclopentadiene, cycloheptene, cyclooctene, 7-oxanorbomene, 7- oxanorbornadiene, cyclooctadiene, cyclododecene, mono- and disubstituted derivatives thereof, especially derivatives wherein the substituent may be C 1-7 alkyl, cyano, diphenylphosphine, trimethylsilyl, methylaminomethyl, carboxylic acid or ester, trifluoromethyl, maleic ester, maleimido and the like, such as
  • Patent No. 6,235,856 the content of which is incorporated herein in its entirety.
  • the invention also contemplates ROMP of mixtures of two or more such monomers in any proportions.
  • Further examples include water-soluble cyclic olefins such as exo-N- (N',N',N'-trimethylammonio)ethyl-bicyclo[2.2.1] hept-5-ene-2,3-dicarboximide chloride or exo-N- (N',N',N'-trimethylammonio)ethyl-bicyclo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide chloride.
  • olefins such as cyclohexenes which have little or no ring strain cannot be polymerized because there is no thermodynamic preference for polymer versus monomer.
  • ROMP of the invention may be carried out in an inert atmosphere for instance by dissolving a catalytic amount of the catalytic component in a suitable solvent and then adding one or more of the said strained cyclic olefins, optionally dissolved in the same or another solvent, to the catalyst solution, preferably under agitation.
  • a ROMP system is typically a living polymerisation process
  • two or more different strained cyclic olefins may be polymerised in subsequent steps for making diblock and triblock copolymers, thus permitting to tailor the properties of the resulting material, provided that the ratio of chain initiation and chain propagation is suitably selected.
  • Solvents that may be used for performing ROMP include all kinds of organic solvents such as protic solvents, polar aprotic solvents and non-polar solvents, as well as supercritical solvents such as carbon dioxide (while performing ROMP under supercritical conditions) and aqueous solvents, which are inert with respect to the strained cyclic olefin and the catalytic component under the polymerization conditions used.
  • Suitable organic solvents include ethers (e.g. dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether or triethylene glycol dimethyl ether), halogenated hydrocarbons (e.g. methylene chloride, chloroform, 1 ,2- dichloroethane, 1 ,1 ,1-trichloroethane or 1 ,1 ,2,2-tetrachloroethane), carboxylic acid esters and lactones (e.g.
  • ethers e.g. dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether or triethylene glycol dimethyl ether
  • ethyl acetate methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, y- butyrolactone, ⁇ -valerolactone or pivalolactone
  • carboxylic acid amides and lactams e.g. N,N- dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, tetramethylurea, hexamethyl- phosphoric acid triamide, ⁇ -butyrolactam, ⁇ -caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone or N-methylcaprolactam
  • sulfoxides e.g.
  • sulfones e.g. dimethyl sulfone, diethyl sulfone, trimethylene sulfone or tetramethylene sulfone
  • aliphatic and aromatic hydrocarbons e.g. petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene, chlorobenzene, o-dichlorobenzene, 1 ,2,4-trichlorobenzene, nitrobenzene, toluene or xylene
  • nitriles e.g.
  • a cationic metal complex species as the catalytic component, the said cationic species being associated with an anion A as described hereinabove.
  • the solubility of the polymer formed by ROMP will depend upon the choice of the strained cyclic olefin, the choice of the solvent and the molecular weight and concentration of the polymer obtained.
  • the strained cyclic olefin is polyunsaturated (e.g. dicyclopentadiene or norbornadiene), the polymer obtained may often be insoluble, whatever the solvent used.
  • Polymerisation temperatures may range from about 0°C to about 120°C, preferably 20°C to 85°C, also depending upon the strained cyclic olefin and the solvent.
  • the duration of polymerisation may be at least about 1 minute, preferably at least 5 minutes, and more preferably at least 30 minutes; the duration of polymerisation may be at most about 24 hours (although longer times may be used at the expense of economic conditions), preferably at most about 600 minutes, and even below 60 minutes.
  • the molar ratio of the strained cyclic olefin to the catalytic component of the invention is not critical and, depending upon the olefin to be polymerised, may be at least about 100, preferably at least 250, more preferably at least 500.
  • the said molar ratio is usually at most about 1 ,000,000, preferably at most 300,000 and more preferably at most 50,000.
  • an oxidation inhibitor and/or a terminating or chain-transfer agent may be added to the reaction mixture, if needed.
  • the choice of the terminating or chain-transfer agent used is not critical to this invention, provided that the said terminating agent reacts with the catalytic component and produces another species which is inactive, i.e. not able to further propagate the polymerisation reaction, under the prevailing conditions (e.g. temperature).
  • a molar excess (with respect to the catalytic component) of a carbonyl compound to the reaction mixture is able to produced a metal oxo and an olefin (or polymer) capped with the former carbonyl functionality; the cleaved polymer can then be separated from the catalyst by precipitation with methanol.
  • Another way of cleaving the polymer from the catalyst may be by the addition of a vinylalkylether.
  • reaction with several equivalents of a chain-transfer agent such as a diene is another way of cleaving the polymer chain, which method does not deactivate the catalytic component, permitting additional monomer to be polymerised, however possibly at the risk of broadening molecular weight distribution.
  • the metal complexes of this invention are stable in the presence of various functional groups, they may be used to catalyze a wide variety of olefins under a wide variety of process conditions.
  • the olefinic compound to be converted by a metathesis reaction may include one or more, preferably at most 2, functional atoms or groups, being for instance selected from the group consisting of hydroxyl, thiol (mercapto), ketone, aldehyde, ester (carboxylate), thioester, cyano, cyanato, epoxy, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, stannyl, disulfide, carbonate, imine, carboxyl, amine, amide, carboxyl, isocyanate, thioisocyanate, carbodiimide, ether (preferably C ⁇ -20 alkoxy or aryloxy), thioether (preferably C ⁇ -20 thioalkoxy
  • the said olefin functional atom or group may be either part of a substituting group of the olefin or part of the carbon chain of the olefin.
  • the metal complexes of this invention are also useful components for catalyzing, at relatively low temperatures (from about 20°C to 80°C), in the presence or absence of a solvent, the ring- closing metathesis of acyclic dienes such as, for instance, diallylic compounds (diallyl ether, diallyl thioether, diallyl phtalate, diallylamino compounds such as diallylamine, diallylamino phosphonates, diallyl glycine esters), 1 ,7-octadiene, substituted 1 ,6-heptadienes and the like.
  • diallylic compounds diallyl ether, diallyl thioether, diallyl phtalate
  • diallylamino compounds such as diallylamine, diallylamino phosphonates, diallyl
  • the metal complexes of this invention may also be used as catalytic components for the preparation of telechelic polymers, i.e. macromolecules with one or more reactive end-groups which are useful materials for chain extension processes, block copolymer synthesis, reaction injection moulding, and polymer network formation.
  • telechelic polymers i.e. macromolecules with one or more reactive end-groups which are useful materials for chain extension processes, block copolymer synthesis, reaction injection moulding, and polymer network formation.
  • An example thereof is hydroxyl-telechelic polybutadiene which may be obtained from 1 ,5-cycooctadiene, 1 ,4-diacetoxy-cis-2-butene and vinyl acetate.
  • a highly functionalized polymer i.e. a polymer with at least two functional groups per chain, is required.
  • olefin coupling may be performed by cross- metathesis comprising the step of contacting a first olefinic compound with such a metal complex in the presence of a second olefin or functionalized olefin.
  • the said first olefinic compound may be a diolefin or a cyclic mono-olefin with a ring size of at least 3 atoms, and the said metathesis cross- coupling is preferably performed under conditions suitable for transforming said cyclic mono-olefin into a linear olefin oligomer or polymer, or said diolefin into a mixture of a cyclic mono-olefin and an aliphatic alpha-olefin.
  • the olefin metathesis reaction can yield a very wide range of end-products including biologically active compounds.
  • the said unsaturated biologically active compound having the formula (VIII) may be a pheromone or pheromone precursor, an insecticide or a insecticide precursor, a pharmaceutically active compound or a pharmaceutical intermediate, a fragrance or a fragrance precursor.
  • a few examples of the said unsaturated biologically active compounds include 1-chloro-5-decene, 8,10- dodecadienol, 3,8,10-dodecatrienol, 5-decenyl acetate, 11-tetradecenylacetate, 1 ,5,9-tetradeca- triene and 7,11-hexadecadienyl acetate.
  • the latter is a pheronome commercially available under the trade name Gossyplure, useful in pest control by effectively disrupting the mating and reproductive cycles of specifically targeted insect species, which may be produced from 1 ,5,9- tetradecatriene, the latter being obtainable from cyclooctadiene and 1-hexene according to the present invention.
  • Gossyplure useful in pest control by effectively disrupting the mating and reproductive cycles of specifically targeted insect species, which may be produced from 1 ,5,9- tetradecatriene, the latter being obtainable from cyclooctadiene and 1-hexene according to the present invention.
  • the Lewis acid co-catalyst (b may be selected from the group consisting of boron trihalides; trialkylboron; triarylboron; organoaluminum compounds; magnesium halides; aluminum halides; titanium or vanadium halides, preferably titanium tetrachloride; antimony and bismuth pentahalides.
  • the Lewis acid co-catalyst (bi) may be an organoaluminum compound selected from the group consisting of tri-n-alkylaluminums; dialkylaluminum hydrides, trialkenylaluminums, alkylaluminum alkoxides, dialkylaluminum alkoxides, dialkylaluminum aryloxides and dialkylaluminum halides.
  • the catalyst activator (b 2 ) may be for instance a diazo compound such as, but not limited to, ethyldiazoacetate and trimethylsilyldiazomethane.
  • ring-opening metathesis polymerization (ROMP) reactions using the catalytic components of the invention may proceed so quickly for olefinic monomers such as dicyclopentadiene or oligomers thereof (i.e. Diels-Alder adducts formed with about 1 to 20 cyclopentadiene units) or mixtures thereof with strained monocyclic or polycyclic fused olefins (e.g. as defined in U. S. Patent No. 6,235,856, the content of which is incorporated herein by reference) that polymerization control could become a problem in the absence of appropriate measures.
  • olefinic monomers such as dicyclopentadiene or oligomers thereof (i.e. Diels-Alder adducts formed with about 1 to 20 cyclopentadiene units) or mixtures thereof with strained monocyclic or polycyclic fused olefins (e.g. as defined in U. S. Patent No. 6,235,856, the content
  • thermoset polymers wherein a liquid olefin monomer and a catalyst are mixed and poured, cast or injected into a mold and wherein on completion of polymerization (i.e. "curing" of the article) the molded part is removed from the mold before any post cure processing that may be required, such as in the Reaction Injection Molding ("RIM”) technique.
  • RIM Reaction Injection Molding
  • the first temperature is about 20°C but, for specific olefins or specific olefin/catalytic component ratios, it may even be suitable to cool the reaction mixture below room temperature, e.g. down to about 0°C.
  • the second temperature is preferably above 40°C and may be up to about 90°C.
  • ROMP using the catalytic components of this invention readily achieve linear or crosslinked polymers of the above-mentioned strained cyclic olefins, such as polynorbornenes and polydicyclopentadienes, with well controlled characteristics, i.e. average molecular weight and molecular weight distribution (polydispersity).
  • norbornene polymers with an average molecular weight ranging from about 200,000 to 2,000,000 and a molecular weight distribution (polydispersity) from about 1.1 to 2.2 may be prepared.
  • Polymerisation in particular when performed in a mold such as in the RIM technique, may occur in the presence of one or more formulation auxiliaries, such as antistatics, antioxidants, ceramics, light stabilizers, plasticizers, dyes, pigments, fillers, reinforcing fibers, lubricants, adhesion promoters, viscosity-enhancing agents and demolding agents, all said auxilaries being well known in the art.
  • formulation auxiliaries such as antistatics, antioxidants, ceramics, light stabilizers, plasticizers, dyes, pigments, fillers, reinforcing fibers, lubricants, adhesion promoters, viscosity-enhancing agents and demolding agents, all said auxilaries being well known in the art.
  • reaction may also advantageously be performed under visible light or ultra-violet light irradiation, e.g. using a source of visible light or ultra-violet light being able to deliver sufficient energy to the reaction system.
  • the catalytic component is used for the atom transfer radical addition (ATRA) reaction of a polyhalogenated alkane CXCI 3 , wherein X is hydrogen, C ⁇ _ 7 alkyl, phenyl or halogen, onto an olefin or diolefin.
  • ATRA atom transfer radical addition
  • Such reaction is preferably performed in the presence of an organic solvent, in a molar excess of the polyhalogenated alkane, and within a temperature range between about 30° and 100°C.
  • Suitable examples of the polyhalogenated alkanes are carbon tetrachloride, chloroform, trichlorophenylmethane and carbon tetrabromide.
  • the catalytic component is used for the atom or group transfer radical polymerization (ATRP) of one or more radically (co)polymerizable monomers.
  • ATRP atom or group transfer radical polymerization
  • concentration of growing radicals exceeds about 10 "6 mole/l, there may be too many active species in the reaction, which may lead to an undesirable increase in the rate of side reactions (e.g. radical-radical quenching, radical abstraction from species other than the catalyst system, and do on).
  • concentration of growing radicals is less than about 10 "8 mole/l, the polymerisation rate may be undesirably slow.
  • concentration of dormant chains is less than about 10 ⁇ 4 mole/l, the molecular weight of the polymer produced may increase dramatically, thus leading to a potential loss of control of its polydispersity.
  • the concentration of dormant species is greater than 1 mole/l, the molecular weight of the reaction product may likely become too small and result in the properties of an oligomer with no more than about 10 monomeric units.
  • a concentration of dormant chains of about 10 "2 mole/l provides a polymer having a molecular weight of about 100,000 g/mole.
  • the various catalytic components of the present invention are suitable for the radical polymerisation of any radically polymerizable, ethylenically or acetylenically unsaturated compound, including acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylic acid amides, methacrylic acid amides, imides (such as N-cyclohexylmaleimide and N- phenylmaleimide), styrenes, dienes or mixtures thereof.
  • any radically polymerizable, ethylenically or acetylenically unsaturated compound including acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylic acid amides, methacrylic acid amides, imides (such as N-cyclohexylmaleimide and N- phenylmaleimide), styrenes, dienes or mixtures thereof.
  • the said compounds are able to provide controlled copolymers having various structures, including block, random, gradient, star-shaped, graft, comb-shaped, hyperbranched and dendritic (co)polymers of various monomer compositions and, consequently, having tailored properties such as heat resistance, scratch resistance, solvent resistance, etc.
  • R 3 ⁇ and R 32 are independently selected from the group consisting of hydrogen, halogen, CN, CF 3 , C ⁇ _ 2 o alkyl (preferably C ⁇ -6 alkyl), ⁇ , ⁇ -unsaturated C 2 - 2 o alkynyl (preferably acetylenyl), , ⁇ -unsaturated C 2-2 o alkenyl (preferably vinyl) optionally substituted (preferably at the ⁇ position) with a halogen, C 3 .
  • R 33 and R 34 are independently selected from the group consisting of hydrogen, halogen (preferably fluorine or chlorine), C 1-6 alkyl and COOR 35 (where R 35 is selected from hydrogen, an alkali metal, or C ⁇ _ 6 alkyl), and at least two of R 31 , R 32 , R 33 and R 34 are hydrogen or halogen.
  • vinyl heterocyclic monomers suitable for ATRP in this embodiment of the sixth aspect of the invention include, but are not limited to, 2-vinyl pyridine, 6-vinyl pyridine, 2-vinyl pyrrole, 5-vinyl pyrrole, 2-vinyl oxazole, 5-vinyl oxazole, 2-vinyl thiazole, 5-vinyl thiazole, 2-vinyl imidazole, 5-vinyl imidazole, 3-vinyl pyrazole, 5-vinyl pyrazole, 3-vinyl pyridazine, 6-vinyl pyridazine, 3-vinyl isoxazole, 3-vinyl isothiazoles, 2-vinyl pyrimidine, 4-vinyl pyrimidine, 6-vinyl pyrimidine, and any vinyl pyrazine, the most preferred being 2-vinyl pyridine.
  • Other preferred monomers include: - (meth)acrylic esters of C 1-20 alcohols, acrylonitrile, cyanoacrylic esters of C -20 alcohols, didehydromalonate diesters of C 1-7 alcohols, vinyl ketones, and - styrenes optionally bearing a C 1-7 alkyl group on the vinyl moiety (preferably at the ⁇ carbon atom) and/or bearing from 1 to 5 substituents on the phenyl ring, said substituents being selected from the group consisting of C ⁇ - 7 alkyl, C 1-7 alkenyl (preferably vinyl or allyl), C ⁇ _ 7 alkynyl (preferably acetylenyl), C 1-7 alkoxy, halogen, nitro, carboxy, C ⁇ -7 alkoxycarbonyl, hydroxy protected with a C ⁇ -7 acyl group, cyano and phenyl.
  • the most preferred monomers for ATRP are methyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, maleimide and styrene.
  • the catalytic component of the invention is more preferably used in combination with one or more initiators having a radically transferable atom or group, since an ATRP catalytic system is based on the reversible formation of growing radicals in a redox reaction between the metal component and an initiator.
  • initiators Xi is preferably bromo which provides both a higher reaction rate and a lower polymer polydispersity.
  • an alkyl, cycloalkyl, or alkyl-substituted aryl group is selected for one of R 3S R 36 and R 37 , the alkyl group may be further substituted with a group Xi such as defined above, in particular a halogen atom.
  • the initiator it is possible for the initiator to serve as a starting molecule for branched, comb-shaped or star-shaped (co)polymers of virtually any type or geometry.
  • One example of such an initiator is a 2,2-bis(halomethyl)-1 ,3-dihalopropane (e.g.
  • R 35 ⁇ R 36 and R 37 is phenyl substituted with from 1 to 5 C ⁇ _ 7 alkyl substituents, each of which may independently be further substituted with a group Xi, e.g. ⁇ , ⁇ '-dibromoxylene, hexakis( ⁇ - chloro- or ⁇ -bromomethyl)benzene.
  • group Xi e.g. ⁇ , ⁇ '-dibromoxylene, hexakis( ⁇ - chloro- or ⁇ -bromomethyl)benzene.
  • Preferred initiators include 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile and C 1-7 alkyl esters of a 2-halo-C 1-7 saturated monocarboxylic acid (such as 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid and the like).
  • a suitable initiator is dimethyl-2- chloro-2,4,4-trimethylgIutarate.
  • Any transition metal complex which can participate in a redox cycle with the initiator and dormant polymer chain, but which does not form a direct carbon-metal bond with the polymer chain such as a complex of ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, nickel or cobalt, is suitable for use in this embodiment of the invention.
  • the amounts and relative molar proportions of the initiator and the transition metal complex of the invention are those which are typically effective to conduct ATRP.
  • the molar proportion of the transition metal complex with respect to the initiator may be from 0.0001 :1 to 10:1 , preferably from 0.1 :1 to 5:1 , more preferably from 0.3:1 to 2:1 , and most preferably from 0.9:1 to 1.1 :1.
  • ATRP according to the invention may be conducted in the absence of a solvent, i.e. in bulk.
  • suitable solvents include ethers, cyclic ethers, alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, acetonitrile, dimethylformamide and mixtures thereof , and supercritical solvents (such as C0 2 ).
  • ATRP may also be conducted in accordance with known suspension, emulsion or precipitation methods.
  • Suitable ethers include diethyl ether, ethyl propyl ether, dipropyl ether, methyl t-butyl ether, di-t-butyl ether, glyme (dimethoxyethane) diglyme (diethylene glycol dimethyl ether), etc.
  • Suitable cyclic ethers include tetrahydrofuran and dioxane.
  • Suitable alkanes include pentane, hexane, cyclohexane, octane and dodecane.
  • Suitable aromatic hydrocarbons include benzene, toluene, o-xylene, m-xylene, p-xylene and cumene.
  • Suitable halogenated hydrocarbons include dichloromethane, 1 ,2-dichloroethane and benzene substituted with 1 to 6 fluorine and/or chlorine atoms, although one should ensure that the selected halogenated hydrocarbon does not act as an initiator under the reaction conditions.
  • ATRP may also be conducted in the gas phase (e.g. by passing the gaseous monomer(s) over a bed of the catalytic system), in a sealed vessel or in an autoclave.
  • (Co)polymerization may be conducted at a temperature from about 0°C to 160°C, preferably from about 60°C to 120°C. Typically, the average reaction time will be from about 30 minutes to 48 hours, more preferably from 1 to 24 hours.
  • (Co)polymerization may be conducted at a pressure from about 0.1 to 100 atmospheres, preferably from 1 to 10 atmospheres.
  • ATRP may also be conducted in emulsion or suspension in a suspending medium for suspending the monomer(s) and while using the metal complex of the invention in combination with a surfactant, so as to form a (co)polymer emulsion or suspension.
  • the suspending medium usually is an inorganic liquid, preferably water.
  • a cationic metal complex species as the catalytic component, the said cationic species being associated with an anion A as described hereinabove.
  • the weight ratio of the organic phase to the suspending medium is usually between 1 :100 and 100:1 , preferably between 1 :10 and 10:1.
  • the suspending medium may be buffered.
  • the surfactant will be selected in order to control the stability of the emulsion, i.e. to form a stable emulsion.
  • the metal catalytic component In order to conduct polymerization in a heterogeneous medium (where the monomer/polymer is insoluble, or only slightly soluble, in the suspension medium, i.e. water or C0 2 ), the metal catalytic component should be- at least partially soluble in the monomer/polymer.
  • ligands are properly selected to allow the catalyst to meet this requirement, such as ligands containing long alkyl chains to increase catalyst solubility in hydrophobic monomers targeted for polymerization, is a successful, controlled ATRP polymerization obtained in the water-borne systems of this embodiment.
  • ligands coordinating the metal in the catalytically active metal complexes of the invention those skilled in the art will be able to make a suitable selection.
  • a key component in the preparation of the stable emulsions of the present embodiment is the use of the surfactant to stabilize the initial monomer suspension/emulsion and growing polymer particles and to prevent unwanted coagulation/flocculation of the particles.
  • Suitable surfactants for this purpose include non-ionic, anionic, and cationic surfactants, with cationic and non-ionic surfactants being preferred in non-buffered solutions.
  • Particularly preferred non-ionic surfactants include polyethylene glycol, polyoxyethylene oleyl ethers and polyoxythylene sorbitan monoalkyls.
  • a preferred cationic surfactant is dodecyltrimethyl ammonium bromide. Regardless of the surfactant used, efficient stirring is preferred to obtain good dispersions or latexes.
  • the surfactant is usually present in a concentration of about 0.01% to 50% by weight based on the total weight of all components introduced into the polymerisation reactor, i.e. suspending medium, monomer(s), surfactant and catalytic system.
  • High solubility in the suspension medium is not a prerequisite for the initiator as may be demonstrated by the use of the poorly water soluble ethyl 2-bromoisobutyrate, to initiate emulsion polymerization. While any order of addition of the initiator and other reaction components can be used, however if the initiator is added to a pre-emulsified reaction mixture, stable latexes are usually obtained. Suitable initiators have been described herein-above in the solvent embodiment of the ATRP process.
  • Initiators can also be macromolecules that contain radically transferable atoms or groups.
  • a special type of such macroinifiators may be water-soluble or even amphiphilic and may, after initiation of the reaction, be incorporated into the polymer particle and may stabilize the growing particle due to the hydrophilic segment of the macroinitiator.
  • the polymer formed may be isolated by known procedures, such as, but not limited to, precipitating in a suitable solvent, filtering the precipitated polymer, then washing and drying the filtered polymer.
  • Precipitation can be typically conducted using a suitable alkane or cycloalkane solvent, such as pentane hexane, heptane, cyclohexane or mineral spirits, or using an alcohol, such as methanol, ethanol or isopropanol, or any mixture of suitable solvents.
  • a suitable alkane or cycloalkane solvent such as pentane hexane, heptane, cyclohexane or mineral spirits
  • an alcohol such as methanol, ethanol or isopropanol, or any mixture of suitable solvents.
  • the precipitated (co)polymer can be filtered by gravity or by vacuum filtration, e.g. using a Buchner funnel and an aspirator.
  • the polymer can then be washed with the solvent used to precipitate the polymer, if desired.
  • the steps of precipitating, filtering and washing may be repeated, as desired.
  • the (co)polymer may be dried by drawing air
  • the dried (co)polymer can then be analyzed and/or characterized e.g. by size exclusion chromatography or NMR spectroscopy.
  • (Co)polymers produced by the catalytic ATRP process of the invention may be useful in general as molding materials (e.g. polystyrene) and as barrier or surface materials (e.g. polymethyl methacrylate). However, since they typically have more uniform properties (in particular molecular weight distribution) than polymers produced by conventional radical polymerization, they will be most suitable for use for specialized applications. For example, block copolymers of polystyrene (PSt) and polyacrylate (PA), e.g. PSt-PA-PSt triblock copolymers, are useful thermoplastic elastomers.
  • PSt polystyrene
  • PA polyacrylate
  • Polymethylmethacrylate/acrylate triblock copolymers are useful, fully acrylic, thermoplastic elastomers.
  • Homo- and copolymers of styrene, (meth)acrylates and/or acrylonitrile are useful plastics, elastomers and adhesives.
  • Either block or random copolymers of styrene and a (meth)acrylate or acrylonitrile are useful thermoplastic elastomers having high solvent resistance.
  • block copolymers in which blocks alternate between polar monomers and non-polar monomers produced by the present invention are useful amphiphilic surfactants or dispersants for making highly uniform polymer blends.
  • Star-shaped (co)polymers e.g. styrene-butadiene star block copolymers, are useful as having high impact resistance.
  • (Co)polymers produced by the catalytic ATRP process of the present invention typically have a number average molecular weight from about 5,000 to 1 ,000,000, preferably from about 10,000 to 250,000, and more preferably from about 25,000 to 150,000. Because ATRP is a living polymerization process, it can be started and stopped practically at will. Further, the polymer product retains the functional group Xi necessary to initiate a further polymerization.
  • a second monomer can then be added to form a second block on the growing polymer chain in a second polymerizing step. Further additional polymerizations with the same or different monomer(s) can be performed to prepare multi-block copolymers. Furthermore, since ATRP is also a radical polymerization, these blocks can be prepared in essentially any order. (Co)polymers produced by the catalytic ATRP process of the present invention have a very low polydispersity index, i.e.
  • the ratio M w /M n of their weight average molecular weight to their number average molecular weight is typically from about 1.1 to 2.4, preferably from 1.15 to 2.0, more preferably from 1.2 to 1.6. Because the living (co)polymer chains retain an initiator fragment including Xi as a terminal group, or in one embodiment as a substituent in a monomeric unit of the polymer chain, they may be considered as end-functional or in-chain functional (co)polymers. Such (co)polymers may thus be converted into (co)polymers having other functional groups (e.g.
  • halogen can be converted into hydroxy or amino by known methods, and nitrile or carboxylic ester can be hydrolyzed to a carboxylic acid by known methods) for further reactions, including crosslinking, chain extension with reactive monomers (e.g. to form long-chain polyamides, polyurethanes and/or polyesters), reactive injection molding, and the like.
  • the present invention further provides silyl derivatives of such complexes, being suitable for covalent bonding to a carrier, especially those complexes wherein the multidentate ligand is a bidentate or tridentate Schiff base, e.g.
  • R' and/or R" of the said general formula is replaced or substituted with a group having the formula: -R 2 o-(CH 2 )n-D-Si-R 2 ⁇ R22R23 (VIII), wherein: - R 2 o is a radical selected from the group consisting of C -7 alkylene, arylene, heteroarylene and C 3 _ o cycloalkylene, the said radical being optionally substituted with one or more R 24 substituents each independently selected from the group consisting of C ⁇ -2 o alkyl, C 2-20 alkenyl, C 2-2 o alkynyl, C 1-20 carboxylate, C ⁇ _ 2 o alkoxy, C 2 - 2 o alkenyloxy, C 2 - 20 alkynyloxy, C 2-2 o alkoxycarbonyl, C ⁇ _ 20 alkylsulfonyl, C -20 alkynylsulfinyl, C 1-2 o
  • silyl derivatives wherein R' is replaced or substituted with a 3-(triethoxysilyl)propyl or 2-(triethoxysilyl)ethyl group.
  • suitable derivatives include shaped organosiloxane copolycondensation products such as disclosed in EP- A-484,755.
  • the invention provides a supported catalyst, especially for use in the above-mentioned catalytic reactions, comprising the product of covalent bonding of (a) a silyl derivative of a metal complex such as defined hereinabove, and (b) a carrier including one or more inorganic oxides or an organic polymeric material.
  • a silyl derivative of a metal complex such as defined hereinabove
  • a carrier including one or more inorganic oxides or an organic polymeric material is selected from silica, alumino-silica, zirconia, natural and synthetic zeolites and mixtures thereof
  • the said organic polymeric carrier is a polystyrene resin or a derivative thereof wherein the aromatic ring is substituted with one or more groups selected from C ⁇ -7 alkyl, C 3- ⁇ 0 cycloalkyl, aryl and heteroaryl.
  • the catalytic component of the sixth aspect of this invention is also useful in the cyclopropanation of ethylenically unsaturated compounds, or the intramolecular cyclopropanation of ⁇ -diazoketones or ⁇ -diazo- ⁇ -ketoesters for producing compounds having one or more cyclopropane structural units in the hydrocarbon chain.
  • This embodiment of the invention is thus useful in one or more manufacturing steps of the following natural and synthetic cyclopropyl- containing compounds.
  • Cyclopropyl-containing compounds may be found in naturally occurring terpenes, steroids, amino-acids, fatty acids, alkaloids and nucleic acids.
  • chrysanthemic acid derivatives (such as pyrethrines) produced in plants are precursors to potent insecticides.
  • the invention is also applicable to making synthetic pyrethroid insecticides such as deltamethrin, as well as sirenine, aristolon, sesquicarene and cyclopropyl derivatives being intermediates in the synthesis of the steroid hirsutene or the antibiotic sarkomycine.
  • Cyclopropyl- containing non-natural compounds also have biological activity, such as Cipro, a powerful anti- anthrax drug, or cyclopropane amino-acids (e.g.
  • 2,3-methanophenylalanine the anti-Parkinson drug 2,3-methano-m-tyrosine, coronatine and coronamic acid.
  • Polycyclopropane fatty acid derivatives isolated from fungi, U-106305 (a cholesteryl ester transfer protein inhibitor) and FR- 900848 (a nucleoside analogue), are also candidates for such synthetic production.
  • Ethylenically unsaturated compounds that may be cyclopropanated according to this invention into the correspondingly cyclopropyl-containing compounds are not particularly limited but include, without restriction, compounds having terminal ethylenic unsaturation such as styrene (which, in the presence of ethyl diazoacetate, may be transformed into ethyl-2-phenylcyclopropanecarboxylate) and substituted derivatives thereof (e.g.
  • Such reaction preferably takes place in the presence of a diazo compound such as, but not limited to, ethyl diazoacetate, cinnamyl diazoacetate, dicyclohexylmethyl diazoacetate, vinyl diazoacetate, menthyl diazoacetate or 1-diazo-6-methyl-5- hepten-2-one, at moderate temperatures usually ranging from about 0°C to 80°C, preferably 20 to 60°C, the reaction time ranging from about 1 to 12 hours, and in a relatively low boiling solvent such as methylene chloride, tetrahydrofuran, ethanol, isopropanol, tert-butanol, L-menthol or water, or mixtures thereof.
  • a diazo compound such as, but not limited to, ethyl diazoacetate, cinnamyl diazoacetate, dicyclohexylmethyl diazoacetate, vinyl diazoacetate, menthyl diazoacetate or 1-diazo-6-methyl-5
  • the diazo compound may be added as such or, in order to eliminate the handling risks associated with its explosive nature, may be generated in situ by reacting an acetoammonium salt with sodium nitrite in the presence of the ethylenically unsaturated compound.
  • a cationic metal complex species as the catalytic component, the said cationic species being associated with an anion A as described hereinabove.
  • the molar ratio of the ethylenically unsaturated compound to the catalytic component is in a range from 200 to 2,000, more preferably from 250 to 1 ,500.
  • the molar ratio of the ethylenically unsaturated compound with respect to the diazo compound is conventional for this kind of reaction, i.e. a molar excess of the former compound.
  • the cyclopropanation of ethylenically unsaturated compounds may optionally be carried out in the presence of a tertiary aliphatic amine, such as triethylamine ortri-n-butylamine, or a heterocyclic amine such as pyridine or lutidine as a co-catalyst.
  • ⁇ -diazo carbonyl compounds such as ⁇ -diazo ketones or ⁇ -diazo- ⁇ -ketoesters may also be performed acccording to similar reaction conditions (temperature, reaction time, substrate/ catalyst ratio) and may result in bicyclic molecules wherein the cyclopropyl group may be fused to another cycloaliphatic group, e.g. a cyclopentanone such as in the synthesis of intermediates of hirsutene or sarkomycin, or a cyclopentyl group when starting from acetylenic ⁇ - diazo ketones.
  • a cyclopentanone such as in the synthesis of intermediates of hirsutene or sarkomycin
  • a cyclopentyl group when starting from acetylenic ⁇ - diazo ketones.
  • the cyclisation of an acetylenic ⁇ -diazo ketone in the presence of a catalytic component of this invention may also lead to the formation of other polycyclic ring systems such as, but not limited to, cyclopentanone fused to a furan, an alkenyl-substituted indenone, a cyclopropyl-substituted indenone, a cyclopentazulenone or a cyclopentadiene fused to indenone.
  • the catalytic component of the sixth aspect of this invention is also useful in the cyclopropenation of alkynes for producing compounds having one or more cyclopropene structural units in the hydrocarbon chain.
  • alkynes having a C 2-7 alkynyl group such as, but not limited to, 1-hexyne, 3,3-dimethyl-1-butyne, phenylacetylene, cyclohexylacetylene, methoxy-methylacetylene and acetoxymethylacetylene which may be converted in good yields into ethylcyclopropene-3-carboxylates in the presence of a diazo compound such as, but not limited to, ethyl diazoacetate, cinnamyl diazoacetate, dicyclohexylmethyl diazoacetate, vinyl diazoacetate, 1- diazo-6-methyl-5-hept'en-2-one or menthyl diazoacetate.
  • a diazo compound such as, but not limited to,
  • the catalytic component of the sixth aspect of this invention is also useful in quinoline synthesis through oxidative cyclisation of 2-aminobenzyl alcohol with ketones (i.e. the so-called Friedlaender reaction). Such reaction preferably takes place with a molar excess of the said ketone, under basic conditions (such as in the presence of an alkali hydroxide), at moderate temperatures usually ranging from about 20 to about 100°C and optionally in the presence of a solvent.
  • the ratio of the 2-aminobenzyl alcohol to the catalytic component is in a range from 100 to 2,000, preferably from 200 to about 1 ,000.
  • a number of alkylarylketones, alkyl heteroarylketones, dialkylketones and benzo-fused cyclic ketones may be used in this process of the invention, including C -7 alkylketones wherein the second hydrocarbon attached to the oxo group may be methyl, pentyl, isopropyl, phenethyl, phenyl, toluyl, anisyl, nitrophenyl, hydroxyphenyl, fluorophenyl, trifluoromethylphenyl, cyanophenyl, naphtyl, furanyl, thiophenyl, pyridyl, and the like.
  • ketones which may be cyclised to quinolines according to this embodiment of the invention include, but are not limited to, acetophenone, 3-methylacetophenone, cyclohexanone, 4-phenylcyclohexanone and propiophenone.
  • Other suitable ketones for this purpose are as disclosed by Cho et al. in Chem. Commun. (2001) 2576-2577.
  • some ketones such as cyclohexanone may be converted into the corresponding quinoline with a yield significantly higher, under equivalent reaction conditions, than achieved by the ruthenium catalyst used in the latter publication.
  • the catalytic component of the sixth aspect of this invention is also useful in the intramolecular epoxidation, including the asymmetric epoxidation, of ethylenically unsaturated compounds, i.e. alkenes, for producing the corresponding epoxides (i.e. oxacyclopropyl-containing compounds).
  • alkenes include for instance, but without limitation, styrene and analogues thereof (such as ⁇ - methylstyrene, p-chorostyrene, p-trifluoromethylstyrene and the like) or cholesterol acetate.
  • Illustrative olefinic starting reactants useful in the asymmetric epoxidation of this invention include those which can be terminally or internally unsaturated and be of straight chain, branched chain, or cyclic structure. Such olefinic reactants may contain from 3 to about 40 carbon atoms and may contain one or more ethylenically unsaturated groups. Moreover, such olefinic reactants may contain groups or substituents which do not essentially adversely interfere with the asymmetric epoxidation process such as carbonyl, carbonyloxy, oxy, hydroxy, oxycarbonyl, halogen, alkoxy, aryl, haloalkyl, and the like.
  • Illustrative olefinic unsaturated compounds include substituted and unsubstituted alpha-olefins, internal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols, and the like, e.g.
  • propylene 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, 2-butene, isoamylene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, cyclohexene, 2-ethylhexene, 3-phenyl-1-propene, 1 ,4-hexadiene, 1 ,7-octadiene, 1 ,5,9- dodecatriene, 3-cyclohexyl-1-butene, allyl alcohol, hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate, aryloates such as vinyl benzoate and the like, 3-butenyl acetate, vinyl propionate, allyl propionate, allyl butyrate, methyl methacrylate, 3-butenyl
  • Epoxidation of the invention may be applied to the synthesis of biologically active molecules such as cis-stilbene oxide (a substrate for microsomal and cytosolic epoxide hydrolase) and isoprostane.
  • biologically active molecules such as cis-stilbene oxide (a substrate for microsomal and cytosolic epoxide hydrolase) and isoprostane.
  • Such epoxidation reaction preferably takes place in the presence of an at least stoechiometric amount (with respect to the ethylenically unsaturated compound) of an oxygen atom source or oxygen-transfer reagent being relatively unreactive toward olefins in the absence of the catalytic system.
  • the said oxygen atom source or oxygen-transfer reagent may be, but without limitation, selected from the group consisting of NaOCI, iodosylmesitylene, Nal0 4 , NBu 4 l0 , potassium peroxymonosulfate, magnesium monoperoxyphthalate, 2,6-dichloropyridine N-oxide and hexacyanoferrate ion.
  • Such epoxidation reaction preferably takes place under conditions and for such time as is needed to epoxidize the olefinic unsaturated compound.
  • Such conditions include, but without limitation: - reaction temperatures usually ranging from about -20° C to about 120° C, preferably from 0° C to 90° C, more preferably from 20 to about 40°C, and/or reaction pressures ranging from about 0.1 to about 70 bars, and/or conducting the reaction in the presence of a solvent for the catalytic system, preferably a relatively low boiling organic solvent selected from the group consisting of saturated alcohols, amines, alkanes, ethers, esters, aromatics and the like, and/or a molar ratio of the ethylenically unsaturated compound to the catalytic component in a range from about 200 to about 20,000, preferably from 500 to 10,000, and/or a molar excess of the oxygen-transfer reagent with respect to the olefinic unsaturated compound.
  • a solvent for the catalytic system preferably a relatively low boiling organic solvent selected from the group consisting of saturated alcohols, amines, alkanes, ethers, esters
  • the catalytic component of the sixth aspect of this invention is also useful in the oxidation of hydrocarbons into alcohols such as, but not limited to, the oxidation of methane (which is known to be more difficult to oxidize than other alkanes) into methanol.
  • hydrocarbons such as, but not limited to, the oxidation of methane (which is known to be more difficult to oxidize than other alkanes) into methanol.
  • methane which is known to be more difficult to oxidize than other alkanes
  • methanol methanol
  • this process is effective for a wide variety of hydrocarbons, it is particularly effective for the oxidation of straight chain and branched chain alkanes and cycloalkanes with 1 to 15 carbon atoms, and arylalkanes such as toluene, xylene and ethylbenzene.
  • the preferred aliphatic hydrocarbons have 1 to 10 carbon atoms, including ethane, propane, butane, isobutane, hexanes, and heptanes; and the preferred cyclic hydrocarbons have 5 to 10 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, cyclooctane and adamantane.
  • This invention is also applicable to a broad range of hydrocarbons containing various substituents to enhance the rate of oxidation.
  • Oxidation according to this invention may be carried out in a liquid phase, mixed solvent system such as water/acetone, water/acetonitrile and/or acetic acid, which is inert to the conditions of the reaction and to oxidation by molecular oxygen.
  • the temperature can range between 20 and 60 °C.
  • the pressure may range from 5 to 20 atmospheres.
  • the hydrocarbon is a solid, liquid or gas, it is either dissolved in the mixed solvent system or is bubbled through the solvent together with air or oxygen before adding the catalytic component of the invention.
  • a concentration ranging from 10 "3 to 10 ⁇ 6 moles of the catalytic component in solution is usually sufficient to achieve the desired oxidation.
  • the reaction time preferably ranges from 30 minutes to 30 hours, more preferably from 1 to 5 hours.
  • the catalytic component of the sixth aspect of this invention is also useful in the oxidation of allylic and benzylic alcohols into carbonyl compounds.
  • the sixth aspect of the present invention also relates to other atom or group transfer reactions such as asymmetric syntheses in which a prochiral or chiral compound is reacted in the presence of an optically active, metal-ligand complex catalyst, in enantiomerically active form, to produce an optically active compound.
  • sulfoxides aziridines, enol esters, nitriles, silanes, silyl ethers, alkanes, phosphonates, alkylboranes, hydroxycarbonyl compounds, ⁇ -cyano carbonyl compounds, carboxyl compounds, arylalkenes, heteroarylalkenes, cyclohexenes, 7-oxanorbornenes, aldehydes, alcohols, primary or secondary amines, amides and the like, have been listed hereinbefore and will be detailed below.
  • the catalytic oxidation of sulfides (into sulfoxides and sulfones), phosphines (into phosphonates), and alcohols or aldehydes into carboxylic acids can be carried out in accordance with conventional oxidation procedures known in the art.
  • optically active carboxylic acids can be prepared by reacting a racemic aldehyde and an oxygen atom source in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic hydrocyanation (or cyanohydration) of ⁇ -ethylenically unsaturated compounds for producing saturated nitriles, or alkynes for producing unsaturated nitriles, or ⁇ , ⁇ -unsaturated aldehydes or ketones for producing ⁇ -cyano carbonyl compounds can be carried out in accordance with conventional procedures known in the art.
  • 1 -phenyl propenone may be transformed into 4-oxo-4-phenyl-butanenitrile, or optically active nitrile compounds can be prepared by reacting a prochiral olefin and hydrogen cyanide in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic hydrosilylation of olefins for producing saturated silanes, or alkynes for producing unsaturated silanes, or ketones for producing silyl ethers, or trialkylsilyl-cyanation of aldehydes (e.g. benzaldehyde) for producing cyanohydrin trialkylsilyl ethers (which may afterwards be hydrolysed into cyanohydrins) can be carried out in accordance with conventional procedures known in the art.
  • optically active silanes or silyl ethers can be prepared by reacting a prochiral olefin or ketone or aldehyde together with a suitable silyl compound under conventional hydrosilylation conditions in the presence of an optically active metal complex catalytic system described herein.
  • Hydrosilylation of olefins, in which a silane reactant R 3 SiH is added to an unsaturated carbon-carbon bond in the presence of a catalyst, as well as hydrosilylation of carbonyl compounds, including aldehydes, ketones and thioketones is extensively reported by Ojima et al. in " The Chemistry of Organic Silicon Compounds ", vol.
  • Catalytic aziridination of imines or alkenes for producing organic compounds having one or more aziridine structural units can be carried out in accordance with conventional procedures known in the art.
  • prochiral olefins can be converted to optically active aziridines under conventional aziridanation conditions in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic hydroamidation of olefins for producing saturated amides can be carried out in accordance with conventional procedures known in the art.
  • optically active amides can be prepared by reacting a prochiral olefin, carbon monoxide, and a primary or secondary amine or ammonia under conventional hydroamidation conditions in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic hydrogenation of olefins into alkanes, or ketones into alcohols can be carried out in accordance with conventional procedures known in the art.
  • a ketone can be converted to an optically active alcohol under conventional hydrogenation conditions in the presence of an optically active metal complex catalytic system as described herein.
  • Substrates that can be hydrogenated in accordance with this embodiment of the invention include, but are not limited to, ⁇ -(acylamino) acrylic acids (thus enantioselectively providing chiral amino-acids), ⁇ - acetamidocinnamic acid, ⁇ -benzamidocinnamic acid, dehydroamino acid derivatives and methyl esters thereof, imines, ⁇ -ketoesters (such as methyl acetylacetate) and ketones.
  • Catalytic aminolysis or hydroamination of olefins for producing saturated primary or secondary amines can be carried out in accordance with conventional procedures known in the art.
  • optically active amines can be prepared by reacting a prochiral olefin with a primary or secondary amine under conventional aminolysis conditions in the presence of an optically active metal complex catalytic system as described herein.
  • the hydroamination reaction may involve a silylazide, e.g., a trialkylsilylazide, and an unsaturated reactant in the form of an alkene or alkyne, i.e. the reaction may proceed first through the formation of a ⁇ -azidoalkylsilane which can then undergo desilylation and reduction of the azide to an amine.
  • Reaction of an alkyne with a trialkylsilylazide produces a vinyl silane that can be further employed in a cross-coupling reaction, in which reduction of the azide intermediate is followed by hydrolysis of the resultant imine to give a ketone, effectively performing a regioselective hydration of a disubstituted alkyne.
  • the present invention is also useful in the silylmetalation of unsaturated compounds, particularly olefins and carbonyl compounds.
  • the adducts formed upon silylmetalation are useful as intermediates in the further synthesis of a variety of compounds.
  • silylboration of a ketone produces a silyl ether containing a quaternary carbon-boron bond
  • subsequent Suzuki cross coupling allows for the introduction of a variety of aryl, vinyl and alkyl halides.
  • the catalytic species of this invention are also applicable to carbometalation reactions such as, but not limited to, the addition of silyl cyanides and allyl silanes to carbonyl compounds and other types of unsaturated substrates.
  • carbometalation reactions such as, but not limited to, the addition of silyl cyanides and allyl silanes to carbonyl compounds and other types of unsaturated substrates.
  • the catalyzed reaction of trimethylsilyl cyanide with an olefin, followed by protodesilylation produces the equivalent of a Markovnikov hydrocyanafion reaction.
  • Transition metal catalyzed cross-coupling using the catalysts and methods of the invention thus provides a stereoselective synthetic route to trisubstituted olefins.
  • Similar reactions can be conducted with allyl silanes in which the activation of the silicon-carbon bond produces a siloxymetal allyl intermediate that can further react with a variety of functional groups (for example, the reaction of an allyl silane with an olefin, followed by protodesilylation).
  • the catalytic species of this invention are also applicable to Suzuki-Miyaura cross-coupling reactions such as, but not limited to, the coupling of an aryl bromide (e.g. 4-bromotoluene) with an arylboronic acid (e.g.
  • Catalytic isomerization of alcohols, preferably allylic alcohols, for producing aldehydes can be carried out in accordance with conventional procedures known in the art.
  • allylic alcohols can be isomerized under conventional isomerization conditions to produce optically active aldehydes in the presence of an optically active metal complex catalytic system described herein.
  • Catalytic Grignard cross coupling of alkyl or aryl halides for producing alkanes or arylalkanes can be carried out in accordance with conventional procedures known in the art.
  • optically active alkanes or arylalkanes can be prepared by reacting a chiral Grignard reagent with an alkyl or aryl halide under conventional Grignard cross coupling conditions in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic hydroboration of olefins such as, but not limited to, 4-methyl-1-pentene
  • alkylboranes and trialkylboranes which may then be oxidised or hydrolysed into alcohols
  • optically active alkyl boranes or alcohols can be prepared by reacting a prochiral olefin and a borane under conventional hydroboration conditions in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic hydride reduction of aldehydes and ketones for producing alcohols can be carried out in accordance with conventional procedures known in the art, i.e. by treating the said aldehyde or ketone with a hydride reagent such as sodium borohydride or alithium aluminum hydride.
  • pentanal may be reduced into 1-pentanol, cyclobutanone into cyclobutanol, and cyclohexane-1 ,4-dione into 1 ,4-cyclohexanediol.
  • Catalytic aldol condensation of saturated carboxyl compounds (aldehydes or ketones) for producing ⁇ , ⁇ -unsaturated carboxyl compounds or ⁇ -hydroxycarbonyl compounds and intramolecular aldol condensation of dialdehydes or diones for producing cyclic ⁇ , ⁇ -unsaturated carboxyl compounds (aldehydes or ketones) can be carried out in accordance with conventional procedures known in the art.
  • optically active aldols can be prepared by reacting a prochiral ketone or aldehyde and a protected enol such as a silyl enol ether under conventional aldol condensation conditions in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic codimerization of alkenes for producing higher saturated hydrocarbons or alkynes for producing higher alkenes can be carried out in accordance with conventional procedures known in the art.
  • optically active hydrocarbons can be prepared by reacting a prochiral alkene and another alkene under codimerization conditions in the presence of an optically active metal complex catalytic system as described herein.
  • Catalytic alkylation, preferably allylic alkylation, of ketones for producing alkylated ketones, preferably allylic ketones can be carried out in accordance with conventional procedures known in the art in the presence of a metal complex catalytic system as described herein.
  • 1 ,3- diphenyl-2-propenyl acetate may be alkylated with a nucleophile such as CH 2 (C0 2 CH 3 ) 2 in the presence of the catalytic component of the invention.
  • Catalytic Diels-Alder reactions such as, but not limited to, the cycloaddition of a conjugated diene onto an ⁇ -ethylenically unsaturated compound for producing optionally substituted cyclohexenes, or the.
  • cycloaddition of furan onto an ⁇ -ethylenically unsaturated compound for producing optionally substituted 7-oxanorbomenes can be carried out in accordance with conventional procedures known in the art in the presence of a metal complex catalytic system as described herein.
  • Catalytic Michael addition of a ketone or a ⁇ -dicarbonyl compound onto an ⁇ , ⁇ -unsaturated carboxyl compound for producing saturated polycarboxyl compounds can be carried out in* accordance with conventional procedures known in the art in the presence of a metal complex catalytic system as described herein, i.e.
  • an enolate ion may undergo conjugate addition to an ⁇ , ⁇ -unsaturated aldehyde or ketone, such as for example the addition of acrolein onto 2,4-pentanedione (acetylacetone) or 2-methylcyclohexanone.
  • an ⁇ , ⁇ -unsaturated aldehyde or ketone such as for example the addition of acrolein onto 2,4-pentanedione (acetylacetone) or 2-methylcyclohexanone.
  • Michael acceptors such as 3-buten-2-one
  • the products of the initial addition are capable of a subsequent intramolecular aldol condensation, the so-called Robinson annulation, e.g. the addition of 3-buten- 2-one onto 2-methylcyclohexanone.
  • Catalytic Heck reactions can be carried out in accordance with conventional procedures known in the art in the presence of a metal complex catalytic system as described herein.
  • the standard Heck reaction involves the reaction of an aryl or heteroaryl halide, e.g. 3-bromoquinoline, with an alkene, commonly an acrylate.
  • An oxidative variant of the Heck reaction proceeds from certain heterocyclic compounds such as indoles, furans and thiophenes such as, but not limited to, N-acetyl-3-methylindole.
  • a reductive variant of the Heck reaction proceeds from certain 3-acylpyridines, 4-acylpyridines and acylindoles, e.g. the reaction of 3-acetylpyridine with triethoxysilylethylene.
  • the permissible prochiral and chiral starting material reactants encompassed by the processes of this invention are, of course, chosen depending on the particular synthesis and product desired. Such starting materials are well known in the art and can be used in conventional amounts in accordance with conventional methods.
  • Illustrative starting material reactants include, for example, aldehydes (e.g. for intramolecular hydroacylation, aldol condensation, and oxidation into acids), prochiral olefins (e.g. for epoxidation, hydrocyanafion, hydrosilylation, aziridination, hydroamidation, aminolysis, cyclopropa-nation, hydroboration, Diels-Alder reaction and codimerization), ketones (e.g.
  • the multidentate ligand and the other ligands are defined as for the main catalytic species of the catalytic system of the fourth aspect of the invention.
  • the multidentate ligand of the metal complex used as a catalytic component is a bidentate or tridentate Schiff base such as defined hereinabove and more specifically as illustrated in figure 1.
  • the catalytic component may also be a five-coordinate metal complex, a salt, a solvate or an enantiomer thereof, comprising a carbene ligand, a multidentate ligand and one or more other ligands, wherein at least one of said other ligands is a constraint steric hindrance ligand having a pKa of at least 15, this kind of metal complex being already described in International Patent Application published as WO 03/062253, the content of which is incorporated herein by reference.
  • the metal is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table, more preferably the metal is selected from the group consisting of iridium, ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt; and/or the multidentate ligand is a bidentate ligand and the metal complex comprises two other ligands, or the multidentate ligand is a tridentate ligand and the metal complex comprises a single other ligand; and/or - the carbene ligand is a benzylidene, vinylidene, indenylidene or allenylidene ligand or a cumuleny
  • one of said other ligands is an anionic ligand, or one of said other ligands is a solvent (which may be selected from the group consisting of protic solvents, polar aprotic solvents and non-polar solvents, including aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides and water) and the complex is a cationic species associated with an anion (which may be selected from the group consisting of hexafluorophosphate, hexafluoroantimoniate, hexafluoroarseniate, tetrafluoroborate, tetra(pentafluorophenyl)borate, perchlorate, alkylsulfonates wherein the alkyl group may be substituted with one or more halogen
  • the multidentate ligand is a bidentate Schiff base having one of the general formulae (IA) or (IB) referred to in figure 1 , wherein Z, R', R" and R"', and optionally R"" and R 5 , are as defined hereinabove in a specific embodiment of the first and second aspects of the present invention.
  • the catalytic component may also be a tetra-coordinated or penta-coordinated metal complex, a salt, a solvate or an enantiomer thereof, comprising: .
  • a tetradentate ligand comprising two Schiff bases, and - optionally a solvent ligand (which may be selected from the group consisting of protic solvents, polar aprotic solvents and non-polar solvents, including aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides and water), the said metal complex then being associated with an anion (which may be selected from the group consisting of hexafluorophosphate, hexafluoroantimoniate, hexafluoroarseniate, tetrafluoroborate, tetra(pentafluorophenyl)borate, perchlorate, alkylsulfonates wherein the alkyl group may be substituted with one or more halogen atoms such as trifluoromethanesulfonate, and arylsulfonates), or an anionic ligand (which may be selected from the group
  • Tetradentate ligands comprising two Schiff bases being suitable for this embodiment include for instance, but without limitation: - the N,N,N,0- tetradentate ligands having the general formula (MIA) shown in figure 3, wherein R and R 2 are independently selected from the group consisting of hydrogen, C -20 alkyl and aryl (in particular phenyl, naphthyl and anthracyl), or R ⁇ and R 2 together form a homocyclic or heterocyclic ring having a total of 3 to 10 atoms, wherein the said C ⁇ -2 o alkyl, aryl, homocyclic and/or heterocyclic groups may be substituted with one or more substituents selected from the group consisting of nitro, halogen, C _ 7 alkoxy, carboxylate, amino, amido, silyl, and siloxyl; each of groups R 3 and R ⁇ 3 is a leaving group, e.g.
  • MIA general formula
  • each of groups R 4 , R 5 , Re and R 7 is independently selected from the group consisting of C _ 7 alkyl, aryl, nitro, halogen, hydrogen, C ⁇ -7 alkoxy, carboxylate, amino; amido, silyl and siloxyl, or two adjacent such groups together form an optionally substituted homocyclic or heterocyclic ring having a total of 3 to 10 atoms; each of groups R 8 , R 9 , Rio, Rn and R 12 is independently selected from the group consisting of hydrogen, C 1-20 alkyl and aryl (in particular phenyl, naphthyl and anthracyl), or R 9 and R 10 together form a homocyclic or heterocyclic ring having a total of 3 to 10 atoms, and/or Rn and R 12 together form a homocyclic or heterocyclic ring having a total of 3 to 10 atoms; the number n of carbon atoms between
  • each of groups R 3 , R 4 , R 5 and R 6 is independently selected from the group consisting of organic moieties, preferably a moiety having a ring structure, more preferably a phenyl group; and G is selected from the group consisting of boron, aryl groups (e.g. phenyl or naphtyl), aliphatic saturated (e.g. C 1-7 alkylene and C 3 . 10 cycloalkylene) and unsaturated (e.g.
  • olefinic chains oligostyrene-maleic anhydride chain
  • complexes formed between these ligands and a metal selected from the group consisting of ruthenium, osmium, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold and silver are novel compounds.
  • the catalytic component which is especially useful in metathesis reactions such as ROMP, as well as in atom or group transfer radical polymerisation (ATRP) of one or more radically (co)polymerisable monomers, atom transfer radical addition (ATRA) and vinylation reaction, may also be a tetra-coordinated or penta- coordinated metal complex, a salt, a solvate or an enantiomer thereof, wherein the metal is selected from the group consisting of iridium, ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt, the said metal complex comprising: at least one bidentate phosphine ligand, and - at least one other ligand
  • each R is independently selected from the group consisting of C ⁇ -7 alkyl and aryl, preferably phenyl, and each cyclic structure represents a ring having 3 to 8 carbon atoms, preferably cyclopentyl or cyclohexyl, which may be substituted within the ring with one or more atoms or groups independently selected from the group consisting of oxygen, sulfur, oxo, thioxo, NR 15 and C(Ri 5 ) 2 , wherein R i5 is selected from the group consisting of C ⁇ -7 alkyl, halo d -7 alkyl, aryl and arylalkyl.
  • IMC general formula
  • the number of atoms between the phosphorus atoms of the two phosphine groups of the said bidentate ligands is not necessarily 4 as shown in formula (IMC) but may also be 3 (spiro phosphines) or 2 (in which case the phosphorus atoms of the two phosphine groups may be linked with each other through a bismethylene or arylene, preferably phenylene, linking group) or else may be higher than 4 (for , instance with the said phosphorus atoms being linked with each other through a ferrocene group).
  • the metal complex of this embodiment may include two bidentate phosphine ligands, the said metal complex then being a cationic species associated with an anion (which may be selected from the group consisting of tetrafluoroborate, tetra(pentafluorophenyl)borate, perchlorate, antimoniohexafluoride, alkylsulfonates wherein the alkyl group may be substituted with one or more halogen atoms such as trifluoromethanesulfonate, and arylsulfonates).
  • an anion which may be selected from the group consisting of tetrafluoroborate, tetra(pentafluorophenyl)borate, perchlorate, antimoniohexafluoride, alkylsulfonates wherein the alkyl group may be substituted with one or more halogen atoms such as trifluoromethanesulfonate, and arylsulfonates
  • Such complexes are novel and may easily be made by reacting at least 2 moles of the bidentate phosphine ligand with one mole of a cationic metal complex including two non-anionic bidentate ligands such as L 3 described hereinabove, in association with the aforesaid anion.
  • the metal complex of this embodiment may include a single bidentate phosphine ligand in association with either (i) two solvent ligands (which may be selected from the group consisting of protic solvents, polar aprotic solvents and non-polar solvents, including aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides and water) or (ii) two anionic ligands such as L 4 described hereinabove and optionally a non-anionic ligand such as an aryl group or (iii) a single anionic ligand such as L 4 described hereinabove (in which case the said metal complex is then a cationic species associated with an anion such as decribed above) or (iv) a single non-anionic bidentate ligand such as L (in which case the said metal complex is then a cationic species associated with an anion A such as decribed above).
  • solvent ligands
  • All of the latter alternatives are novel complexes when the metal is selected from the group consisting of osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt.
  • the alternative (i) hereinabove also relates to novel complexes when the metal is selected from the group consisting of rhodium, ruthenium, palladium and platinum.
  • the catalysts of the present invention thus have utility in the whole range of chemical reactions and processes listed and explained in detail hereinbefore.
  • agrochemicals or therapeutically active substances belonging to various therapeutic classes such as, but not limited to, naproxen (an anti-inflammatory agent); prostaglandins; alkaloids; morphine and salts thereof; morphine analogues including morphinan, benzylmorphin and methoxy-N-methylmorphinan (dextromethorphan); levamisole (an anthelmintic); levofloxacin; indinavir (a HIV protease inhibitor); or intermediates in a variety of synthetic fragrances such as, but not limited to, citronellol.
  • naproxen an anti-inflammatory agent
  • prostaglandins alkaloids
  • morphine and salts thereof morphine analogues including morphinan, benzylmorphin and methoxy-N-methylmorphinan (dextromethorphan); levamisole (an anthelmintic); levofloxacin; indinavir (a HIV protease inhibitor); or intermediates in a variety of synthetic
  • the invention further provides an at least penta-coordinated metal complex, a salt, a solvate or an enantiomer thereof, comprising: a tetradentate ligand comprising two Schiff bases, wherein the nitrogen atoms of said two Schiff bases are linked with each other through a C ⁇ profession 7 alkylene or arylene linking group A; and one or more non-anionic ligands L 7 selected from the group consisting of (i) imidazoles and trisubstituted phosphines PR 3 wherein R is a radical selected from the group consisting of C 1-7 alkyl, C 3-10 cycloalkyl, aryl and heteroaryl; and (ii) aromatic and unsaturated cycloaliphatic groups, preferably aryl, heteroaryl and C 4 .
  • a tetradentate ligand comprising two Schiff bases, wherein the nitrogen atoms of said two Schiff bases are linked with each other through a C ⁇ profession 7 alkylene or arylene
  • each of the substituting radicals R and the ligand L 7 may, independently from each other, be any of the above-mentioned groups with any of the substituents listed for such groups, including any of the individual meanings for such groups or substituents which are listed in the definitions given hereinabove.
  • the non-anionic ligand L 7 has constraint steric hindrance such as, but not limited to, mono- or polysubstituted phenyl, e.g. xylyl, cumenyl, cymenyl or mesityl.
  • the substituting radicals R also have constraint steric hindrance such as, but not limited to, phenyl or cyclohexyl.
  • the at least penta-coordinated metal complex according to this seventh aspect of the invention preferably is a monometallic complex.
  • the metal is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table.
  • each said non- anionic ligand L 7 may be is cymene.
  • the C -7 alkylene or arylene linking group A may be substituted with one or more substituents preferably selected from the group consisting of chloro, bromo, trifluoromethyl and nitro.
  • the C ⁇ -7 alkylene or arylene linking group A, together with the two linked nitrogen atoms, is derived from o-phenylenediamine, ethylenediamine, 1,3- diaminopropane, 1 ,4-diaminobutane, 1 ,5-diaminopentane, 1 ,6-diaminohexane or 1,7- diaminoheptane.
  • each Schiff base of the tetradentate ligand is derived from salicylaldehyde or acetylacetone, wherein the salicylidene or acetylidene group included in each such Schiff base may be substituted with one or more substituents preferably selected from the group consisting of chloro, bromo, trifluoromethyl and nitro.
  • Suitable but non limiting examples of tetradentate ligands for this seventh aspect of the invention have one of the general formulae (IIA), (IIB) and (IIC) shown in figure 2. More specific examples include the so-called salen (i.e. bis(salicylaldehyde) ethylenediamine), saloph (i.e.
  • the substituents X are preferably selected from the group consisting of chloro, bromo, trifluoromethyl and nitro.
  • the substituents Y are preferably selected from the group consisting of chloro, bromo, trifluoromethyl and nitro, and the substituents X are preferably selected from the group consisting of hydrogen, methyl, fluoro, chloro, bromo, trifluoromethyl and nitro.
  • the substituents Y are preferably selected from the group consisting of hydrogen and methyl.
  • a preferred tetradentate ligand is ⁇ /, ⁇ /-bis(5-nitro-salicylidene)-ethylenediami ⁇ e.
  • Other suitable ligands include N,N'-1,2-cyclohexylenebis(2-hydroxyacetophenonylideneimine), 1,2- diphenylethylenebis(2-hydroxy-acetophenonylideneimine) and 1,1 '-binaphtalene-2,2'-diaminobis(2- hydroxyaceto-phenonylideneimine), all being described in Molecules (2002) 7:511-516.
  • the at least penta-coordinated metal complex according to this seventh aspect of the invention may be made by reacting a suitable tetradentate ligand such as defined hereinabove with a preferably bimetallic complex of the desired metal, more preferably a homobimetallic complex wherein the desired metal is coordinated with a non-anionic ligand L 7 and at least one anionic ligand, such as [RuCI 2 (p-cymene)] 2 , [RuCI 2 (COD)] 2 or [RuCl 2 (NBD)] 2 , wherein COD and NBD respectively mean cyclooctadiene and norbornadiene.
  • a suitable tetradentate ligand such as defined hereinabove
  • a preferably bimetallic complex of the desired metal more preferably a homobimetallic complex wherein the desired metal is coordinated with a non-anionic ligand L 7 and at least one anionic ligand, such as [RuCI 2 (p-cymene
  • his invention also provides a catalytic system comprising: (a) as the main catalytic species, an at least penta-coordinated metal complex according to the seventh aspect described hereinabove, and (b) one or more co-catalysts or initiators for the main catalytic species.
  • the co-catalyst or initiator may be selected from amines, preferably secondary amines; organoaluminum compounds; and initiators having a radically transferable atom or group.
  • the initiator having a radically transferable atom or group may preferably be selected from the group of initiators having the formula wherein: Xi is selected from the group consisting of halogen, OR 38 (wherein R 38 is selected from C ⁇ .
  • this invention also provides a supported catalyst for use in a heterogeneous catalytic reaction, comprising: (a) a catalytically active at least penta-coordinated metal complex according to the seventh aspect or a catalytic system according to the eighth aspect described hereinabove, and (b) a supporting amount of a carrier suitable for supporting said catalytically active metal complex or catalytic system (a).
  • Said carrier may be selected from the group consisting of porous inorganic solids, such as amorphous or paracrystalline materials, crystalline molecular sieves and modified layered materials including one or more inorganic oxides, and organic polymer resins, all of them being as defined hereinabove with respect to the fifth aspect of the invention.
  • the at least penta-coordinated metal complex according to the seventh aspect of the invention is useful as a catalytic component in a reaction involving the transfer of an atom or group to an olefin or another reactive substrate.
  • the said reaction comprises the step of reacting the olefin or reactive substrate with a second substrate under suitable reaction conditions in the presence of the said catalytic component, the second substrate being a suitable donor for the atom or group to be transferred.
  • the said reaction may be, but without limitation, selected from the group consisting of: atom or group transfer radical polymerisation of one or more radically (co)polymerisable monomers, especially mono- and diethylenically unsaturated monomers; atom transfer radical addition (the latter being as explained in the background of the invention), e.g. the addition of a polyhalomethane having the formula CX n H 4 .
  • X is halogen and n is an integer from 2 to 4, onto an ethylenically unsaturated compound to produce the corresponding saturated polyhalogenated adduct, including for instance the addition of carbon tetrachloride or chloroform onto an ⁇ -olefin; vinylation reaction, i.e. the reaction of a mono- or di-alkyne (e.g. phenylacetylene or 1 ,7- octadiyne) with a monocarboxylic acid (e.g.
  • this invention provides useful catalysts species being penta-coordinated metal complexes, salts, solvates or enantiomers thereof, comprising: a bidentate Schiff base ligand (such as above defined), an anionic ligand (such as above defined), a non-anionic ligand (such as above defined), and - a Fischer carbene ligand.
  • a bidentate Schiff base ligand such as above defined
  • an anionic ligand such as above defined
  • a non-anionic ligand such as above defined
  • Fischer carbene ligands are well known in the art and are consistently defined, e.g.
  • said pi-donor group should be selected from the group consisting of C -7 alkoxy, C 3-10 cycloalkoxy, aryloxy, arylalkyloxy, heterocyclic-substituted alkyloxy, thio C 1-7 alkyl, thio C 3- 0 cycloalkyl, thioaryl, arylalkylthio and heterocyclic-substituted alkylthio.
  • the Fischer carbene ligand in this aspect of the present invention should be a C -7 alkoxyvinylidene, most preferably ethoxyvinylidene.
  • the bidentate Schiff base ligand has one of the general formulae (IA) or (IB) referred to in figure 1 , wherein: Z is selected from the group consisting of oxygen, sulphur, selenium, NR"", PR"", AsR"" and SbR"", wherein R"" is a radical selected from the group consisting of hydrogen, C 1-7 alkyl, C 3-10 cycloalkyl, aryl and heteroaryl; - R" and R"' are each a radical independently selected from the group consisting of hydrogen, C 1-6 alkyl, C 3 8 cycloalkyl, aryl and heteroaryl, or R" and R'" together form an aryl or heteroaryl radical, each said radical being optionally substituted with one or more, preferably
  • the non-anionic ligand is selected from the group consisting of trisubstituted phosphines PR 3 wherein R is a radical selected from the group consisting of C 1-7 alkyl, C 3- 0 cycloalkyl, aryl and heteroaryl.
  • the anionic ligand is selected from the group consisting of C ⁇ -20 carboxylate, C 1-20 alkoxy, C 2-2 o alkenyloxy, C 2-2 o alkynyloxy, aryloxy, C -20 alkoxycarbonyl, C 1-7 alkylthio, C ⁇ -20 alkylsulfonyl, C ⁇ _ 2 o alkylsulfinyl C _ 20 alkylsulfonate, arylsulfonate, C ⁇ -20 aikylphosphonate, arylphosphonate, C ⁇ -20 alkylammonium, arylammonium, alkyldiketonate, aryldiketonate, halogen, nitro and cyano.
  • Fischer carbene containing penta-coordinated metal complexes include, but are not limited to, complexes such as: chloro-tricyclohexylphosphino-ethoxyvinyIidene-N,0[N-(4-bromo-2,6-dimethylphenyl)-((2- phenoxy)-1-phenyl)iminomethane]-ruthenium, chloro-tricyclohexylphosphino-ethoxyvinylidene-N,0[N-(4-bromo-2,6-dimethylphenyl)-((2- phenoxy-5-nitro)-1-phenyl)iminomethane]-ruthenium, chloro-tricyclohexylphosphino-ethoxyvinylidene-N,0[N-(2,6-diisopropylphenyl)-((2- phenoxy)-1-phenyl)iminomethane]-ruthenium, - tol
  • Such Fischer carbene containing penta-coordinated metal complexes proved to be efficient as catalytic components for performing reactions involving the transfer of an atom or group to an olefin or another reactive substrate (such reactions being as illustrated above), especially in the atom transfer radical polymerisation of monomers like styrene and (meth)acrylates.
  • this invention provides useful catalysts species being penta-coordinated metal complexes, salts, solvates or enantiomers thereof, comprising:
  • metal complexes according to this aspect of the present invention may be monometallic or bimetallic. They may also be grafted to a suitable carrier such as a porous inorganic solid. Metal complexes according to this aspect of the present invention proved to be efficient as catalytic components for performing olefin or acetylene metathesis reactions such as, but not limited to, RCM and ROMP.
  • this invention provides useful catalysts species being penta-coordinated metal complexes, salts, solvates or enantiomers thereof, comprising:
  • a carbene ligand having a terminal hydrocarbylsilyl group such as, but not limited to, trialkylsilyl (e.g. trimethylsilyl), triarylsilyl and tricycloalkylsilyl.
  • Metal complexes according to this aspect of the present invention proved to be efficient as catalytic components for performing olefin or acetylene metathesis reactions such as, but not limited to, RCM and ROMP.
  • NMR proton nuclear magnetic resonance
  • IR infrared spectrophotometry
  • N-(4-bromo-2,6-dimethyl)-2-hydroxy-3-tertbutyl-1-phenylmethaneimine (Schiff base 1-B) obtained (yellow oil, 2.8 g, yield 79 %) from 1.71 ml 3-ferf-butyl-2-hydroxybenzaldehyde and 2 g 4-bromo-2,6-dimethylaniline.
  • N-(4-bromo-2,6-dimethylphenyl)-2-hydroxy-1-phenylmethaneimine (Schiff base 1-C) obtained (yellow powder, 2.83 g, yield 93 %) from 1.065 ml salicylaldehyde and 2 g 4- bromo-2,6-dimethylaniline.
  • N-(4-bromo-2,6-dimethylphenyl)-2-hydroxy-4-nitro-1-phenylmethaneimine (Schiff base 1-D) obtained as a dark yellow powder from 1.67 g 4-hydroxy-3-nitrobenzaldehyde and 2 g 4- bromo-2,6-dimethylaniline.
  • N-(2,6-diisopropyIphenyl)-2-hydroxy-4-nitro-1-phenylmethaneimine (Schiff base 1-E) obtained as a yellow powder from 1.065 ml salicylaldehyde and 1.88 ml 2,6- diisopropylaniline.
  • example 3 (obtained from Schiff base 1-E and methyllithium): 2H), 1.12 (d, 12 H); H), 3.10 (sept, 1H), : 3052, 2980, 2970, 087, 976, 930, 850
  • example 6 obtained from Schiff base 1-A in the second step
  • example 7 obtained from Schiff base 1-A and methyllithium
  • 1 H-NMR ⁇ 7,693 (s, 1H); 7,047-6,15 (m, 6H); 2,723 (sept, 2H); 1 ,404 (s, 9H); 1 ,31 (d, 12H); 4,95 (d, 1 H); 4,55 (d, 1 H); 4,48 (d, 1 H); 4,42 (d, 1H); 2,426 (sept, 1H); 1 ,596 (s, 3H); 1 ,050 (d, 6H) and 0,04 (s, 3H) ppm; 13 C- NMR: ⁇ 163,047; 152,815; 137,314; 134,565; 131 ,872; 127,227; 124,148; 122,06; 115,546; 35,619; 26,934; 103,04; 91 ,77; 88,36; 85
  • EXAMPLE 12 - ring opening metathesis polymerisation of norbornene Ring opening metathesis polymerisation of norbornene was performed during 18 hours at 85°C in methylene chloride as a solvent, while using the Schiff base substituted ruthenium complexes of examples 6 to 8 and the bimetallic Schiff base substituted ruthenium complexes of examples 10 and 11 as catalysts in a molar ratio norbomene/catalyst equal to 225, and optionally in the presence of a co-catalyst being either triethylaluminum or diethylaluminum chloride (in a molar ratio 6:1 with respect to ruthenium) or an activator being trimethylsilyldiazomethane (TMSD, in a molar ratio 3:1 with respect to ruthenium).
  • the following table 2 indicates the polymerisation yield (%) achieved (ND: not determined) for each complex used.
  • the norbornene polymer obtained obtained in the presence of the complex of example 8 and diethylaluminum chloride was analysed and found to have a number average molecular weight of 450,000 and a molecular weight distribution (polydispersity) of 2.1.
  • EXAMPLE 13 - ring opening metathesis polymerisation of norbornene under irradiation
  • the experiment of example 12 is repeated with the ruthenium complex of example 8 without any co-catalyst or activator but at 20°C under irridiafion by a source of visible light.
  • the polymerisation yield observed after 20 hours is 86%.
  • EXAMPLE 14 monometallic ruthenium complex coordinated with a nitrosubstituted salen ligand
  • a monometallic ruthenium complex coordinated with a ⁇ /, ⁇ /'-bis(5-nitro-salicylidene)- ethylenediamine ligand was made according to the general method disclosed above from a ruthenium precursor [RuC L ⁇ .wherein L is cymene.
  • This complex was then tested in the atom transfer radical polymerisation of various olefins performed in 1 ml toluene during 17 hours at 85 °C (acrylates) or 110°C (styerene) while using: as an initiator, ethyl-2-methyl-2-bromopropionate (when the monomer is a methacrylate) or (l-bromoethyl)benzene (when the monomer is styrene), and a molar ratio [catalyst]/[initiator]/[monomer] equal to 1 :2:800.
  • Table 3 indicates the name of the olefin involved, the polymerisation yield (expressed in %), the average number molecular weight M n and the polydispersity index M w /M n .
  • Table 3 Olefin Yield M n M w /M n Methylmethacrylate (MMA) 69 41 ,000 2.2
  • IBMA Isobutylmethacrylate
  • Sty Styrene
  • EXAMPLE 22 atom transfer radical polymerisation of methyl methacrylate and styrene Complexes of examples 19 to 21 were tested as in example 14. Results are given in table 5.
  • the ligand 1 (N-methyl-2-hydroxy-1-phenylmethaneimine) was characterized by means of proton NMR, the corresponding spectrum being shown in figure 4.
  • each ruthenium complex was characterized by means of proton NMR performed with CDCI 3 at 25°C as follows: complex (example 24) obtained from the ligand 1 of example 23: ⁇ " at 8.35 (1 H), 6.85-7.20 (4H), 3.12 (3H), 5.47 (2H), 5.34 (2H), 2.92 (1 H), 2.17 (3H) and 1.25 (6H) ppm; - complex (example 25) obtained from the ligand 2 of example 23: ⁇ at 8.25 (1 H), 6.85-7.00 (4H), 2.54 (9H), 5.46 (2H), 5.32 (2H), 2.75 (1 H), 2.24 (3H) and 1.25 (6H) ppm; complex (example 26) obtained from the ligand 3 of example 23: ⁇ " at 7.76 (1 H), 7.20-7.46 (4H), 6.92-7.02 (5H), 5.49 (2H), 5.34 (2H), 2.92 (1 H), 2.16 (3H), and 1.25 (6H) ppm; complex (example 27) obtained from the ligand
  • EXAMPLE 34 cyclopropanation of styrene with ethyldiazoacetate
  • the catalyst was first dissolved in toluene, then styrene was added to the solution. Ethyl diazoacetate was dissolved in toluene and then added to the mixture of styrene and catalyst through a peristaltic pump over a period of 4 hours, after which the reaction mixture was heated to 60°C for 6 hours (with the following exceptions: heating time was increased to 10 hours when using the complexes of examples 28 and 30 as catalysts). After the reaction time, reaction products were analysed by gas chromatography, and conversion (expressed as a percentage) and diastereoselectivity (expressed as a cis:trans ratio) were calculated according to standard practice. Results are reported in table 7. Table 7
  • EXAMPLE 35 oxidative cyclisation of 2-aminobenzyl alcohol with ketones
  • the oxidative cyclisation of 2-aminobenzyl alcohol with various ketones i.e. the so-called modified Friedlaender quinoline synthesis
  • one of the ruthenium complexes of examples 25 to 33 as a catalyst and dioxane as a solvent was performed while using the following amounts: catalyst: 10 ⁇ mole, 2-aminobenzyl alcohol: 1 mmole, and ketone: 2 mmoles, i.e. an alcohol / catalyst ratio of 100 / 1.
  • EXAMPLE 36 - ring opening metathesis polymerisation in the presence of a co-catalyst at higher norbornene/catalvst molar ratios
  • Ring opening metathesis polymerisation of norbornene was performed as in example 12, in the presence of diethylaluminum chloride (in a molar ratio 6:1 with respect to ruthenium) as a co- catalyst, except that the norbornene/catalyst molar ratio was increased to 900 and 6,000 respectively, as shown in table 9 which also indicates the polymerisation yield (%) achieved (ND: not determined) for each complex used and each norbornene / catalyst ratio.
  • the norbornene polymers obtained obtained in the presence of the complex of example 8 were analysed and found to have the following molecular weight M n and polydispersity index M w /M n : - at a norbornene/catalyst molar ratio of 900: M n is 2,000,000 and M w /M n is 1.32; - at a norbornene/catalyst molar ratio of 6,000: M n is 1 ,350,000 and M w /M n is 1.33.
  • EXAMPLE 38 - ring opening metathesis polymerisation of strained cyclic olefins in the presence of a co-catalvst Ring opening metathesis polymerisation was performed as in example 12, in the presence of diethylaluminum chloride (in a molar ratio 6:1 with respect to ruthenium) as a co-catalyst, except that norbornene was replaced as a monomer by the strained cyclic olefins shown in table 11 which also indicates the polymerisation yield (%) achieved for each complex used and each monomer.
  • EXAMPLE 39 - atom transfer radical polymerisation of MMA in the presence of a co-catalvst
  • the ruthenium complexes of examples 8, 10 and 11 were tested for the polymerisation of methyl methacrylate as in example 14, but in the presence of di-n-butylamine as an additive used in a molar ratio of 4:1 with respect to the ruthenium catalyst.
  • Table 12 indicates, for each complex used, the polymerisation yield (expressed in %), the average number molecular weight M n and the polydispersity index M w /M n . of the resulting polymer.
  • Table 12 indicates, for each complex used, the polymerisation yield (expressed in %), the average number molecular weight M n and the polydispersity index M w /M n . of the resulting polymer.
  • EXAMPLE 40 - atom transfer radical polymerisation of styrene in the presence of a co-catalvst
  • the ruthenium complexes of examples 8, 10 and 11 were tested for the polymerisation of styrene as in example 14, but in the presence of di-n-butylamine as an additive used in a molar ratio of 4:1 with respect to the ruthenium catalyst.
  • Table 13 indicates, for each complex used, the polymerisation yield (expressed in %), the average number molecular weight M n and the polydispersity index M w /M n of the resulting polymer.
  • Table 13 Styrene Yield M n M w /M n Complex 8 100 49,000 1.83 Complex 10 99 53,000 1.77 Complex 11 66 38,000 1.86
  • EXAMPLE 41 - atom transfer radical polymerisation of styrene in the presence of a co-catalvst
  • the ruthenium complexes of examples 8, 10 and 11 were tested for the polymerisation of styrene as in example 14, but in the presence of tri-isopropylaluminum as an additive used in a molar ratio of 4:1 with respect to the ruthenium catalyst.
  • Table 14 indicates, for each complex used, the polymerisation yield (expressed in %), the average number molecular weight M n and the polydispersity index M w /M n of the resulting polymer.
  • EXAMPLE 42 vinylation reaction with a ruthenium catalyst
  • a monocarboxylic acid indicated in table 15
  • 4.4 mmole of a terminal alkyne indicated in table 15
  • 0.04 mmole of the ruthenium catalyst of example 6 were transferred into a 15 ml glass vessel containing 3 ml toluene. Then the reaction mixture was heated for 10 hours at 110°C under an inert atmosphere. The total yield was determined with Raman spectroscopy by following the decreasing intensity of the vibration v c ⁇ c of the terminal alkyne and using a calibration curve.
  • EXAMPLE 43 - atom transfer radical polymerisation Complexes were prepared, by analogy with a procedure described by Carter et al. in Polyhedron (1993) 12:1123, by reacting two equivalents of a saturated aliphatic monoamine (identified in table 9) with one equivalent of [RuCI 2 (p-cymene)] 2 . These complexes were then tested in the polymerisation of methyl methacrylate (MMA) or styrene using the same conditions as in example 14, except reaction time which was 8 hours. Results are given in table 16 and illustrate the influence of the choice of the aliphatic amine on the yield, molecular weight and polydispersity of polymethylmethacrylate.
  • EXAMPLE 44 preparation of a heterogeneous catalyst by anchoring a dichloro-p-cymenyl-amino ruthenium complex onto a mesoporous crystalline molecular sieve
  • the synthesis of this solid-supported catalyst was effected by a method similar to that shown in figure 7 of WO 03/062253.
  • the mesoporous crystalline molecular sieve MCM 41 (having a specific surface of 1220 m 2 /g) was reacted with aminopropyltriethoxysilane at 100°C in the presence of toluene as a solvent.
  • EXAMPLE 45 Atom transfer Radical Polymerisation in the presence of a supported catalyst All reagents and solvents were dried, distilled and stored under nitrogen at - 20 °C with conventional methods. Then, 0.0116 mmole of the supported catalyst produced in example 37 was placed in a glass tube (in which the air was expelled by three vacuum-nitrogen cycles) containing a magnet bar and capped by a three-way stopcock.
  • styrene (as the monomer) and 1- bromoethyl benzene (as the initiator, diluted in toluene) were added to the catalyst in such amounts that the molar ratio [catalyst]/[initiator]/[monomer] was 1 :2:800. All liquids were handled under argon with dried syringes. The reaction mixture was heated for 17 hours at 110°C and then, after cooling, diluted in chloroform and poured in 50 ml methanol under vigorous stirring, after which the precipitated polystyrene was filtered, dried under vacuum at 50°C during 4 hours and analysed.
  • Polystyrene yield was 99%, molecular weight (M n ) was 77,000 and polydispersity index (M w /M n ) was 1.68.
  • M n molecular weight
  • M w /M n polydispersity index
  • EXAMPLE 46 preparation of ruthenium metal complexes wherein the Schiff base ligand contains a terminal silyl moiety
  • Ruthenium metal complexes wherein the Schiff base ligand contains a tenninal silyl moiety were prepared according to the three-steps procedure shown in the following scheme.
  • a Schiff base ligand containing a terminal silyl (e.g. triethoxy-silyl) moiety was prepared by reacting 3-triethoxypropylamine with 2-hydroxybenzaldehyde during 2 hours at 25 "C in THF as a solvent.
  • step (ii) The resulting Schiff base ligand was then reacted at room temperature in step (ii) with thallium ethoxide during 1 hour and then with dichloro-(3-phenyl-1-indenylidene)- bis(tricyclohexylphosphino)-ruthenium during 4 hours.
  • step (iii) The resulting monometallic ruthenium complex [90] was then transformed in step (iii) into a heterogeneous catalyst [91] by reaction at 25 °C with dry MCM-41 in methylene chloride during 24 hours, or in step (iv) into a bimetallic ruthenium complex [92] by the addition of 0.5 molar equivalent of [RuCI 2 (p-cymene)] 2 .
  • the latter complex [92] was further characterised by proton and carbon nuclear magnetic resonance as follows: m, H), H), 1.8
  • EXAMPLE 47 - ring opening metathesis polymerisation of norbornene monomers Ring opening metathesis polymerisation of various norbornene monomers was performed during 4 hours at 80 °C in toluene (1 ml) as a solvent, while using the Schiff base ruthenium complexes of example 46 as catalysts in a molar ratio norbornene monomer/catalyst equal to 800.
  • the following table 17 indicates the polymerisation yield for each complex and, when the heterogeneous catalyst [91] was used, the properties (number average molecular weight, polydispersity) of the polymer formed. Table 17
  • EXAMPLE 50 - ring opening metathesis polymerisation of strained cyclic monomers Ring opening metathesis polymerisation of R-substituted norbornene monomers (wherein R has the meaning indicated in table 19), or cyclooctene, was performed at 80 °C in toluene as a solvent, while using the Schiff base ruthenium complex of example 49 as a catalyst in a molar ratio monomer/catalyst equal to 800 (except for cyclooctene: molar ratio 250).
  • Table 19 indicates the polymerisation yield for each complex and the properties (number average molecular weight, polydispersity) of the polymer formed. Table 19

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des complexes métalliques utiles comme catalyseurs dans des réactions de métathèse d'oléfine, de polymérisation radicalaire à transfert d'atome ou de groupe ou d'addition et de vinylation.
PCT/BE2004/000146 2003-10-16 2004-10-15 Complexes metallliques a base de schiff utilisables comme catalyseurs en synthese organique WO2005035121A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP03447257.1 2003-10-16
EP03447257 2003-10-16
US52901003P 2003-12-12 2003-12-12
US60/529,010 2003-12-12

Publications (2)

Publication Number Publication Date
WO2005035121A2 true WO2005035121A2 (fr) 2005-04-21
WO2005035121A3 WO2005035121A3 (fr) 2005-06-30

Family

ID=34436743

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BE2004/000146 WO2005035121A2 (fr) 2003-10-16 2004-10-15 Complexes metallliques a base de schiff utilisables comme catalyseurs en synthese organique

Country Status (1)

Country Link
WO (1) WO2005035121A2 (fr)

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1757613A1 (fr) * 2005-08-22 2007-02-28 Viacatt N.V. Complexes en métal multi coordonné pour l'usage dans des réactions de metathesis
CN100586966C (zh) * 2007-12-06 2010-02-03 中国科学院长春应用化学研究所 一种双水杨醛亚胺钒烯烃聚合催化剂及制备方法和应用
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7687635B2 (en) 2002-01-22 2010-03-30 Telene S.A.S. Metal complexes useful in metathesis and other reactions
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
WO2012076542A1 (fr) * 2010-12-07 2012-06-14 Solvay Sa Polymérisation radicalaire régulée de monomères halogénés
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
CN103949288A (zh) * 2014-04-10 2014-07-30 北京化工大学 分子筛负载的Cu-Co希夫碱配合物及其制备方法和应用
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
EP2778154A1 (fr) * 2013-03-13 2014-09-17 Evonik Industries AG Génération in situ de catalyseurs de ruthénium pour la métathèse d'oléfine
US8927670B2 (en) 2005-08-22 2015-01-06 Rimtec Corporation Multicoordinated metal complexes for use in metathesis reactions
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
WO2016000242A1 (fr) 2014-07-03 2016-01-07 Guang Ming Innovation Company (Wuhan) Catalyseurs à base de métaux de transition du groupe 8 ainsi que leurs procédés de fabrication et leurs procédés d'utilisation dans la réaction de métathèse
DE102015201292A1 (de) * 2015-01-26 2016-07-28 Henkel Ag & Co. Kgaa Organische Zinkkomplexe als Katalysatoren für Kondensationsreaktionen
CN106046207A (zh) * 2016-05-31 2016-10-26 北京理工大学 一种苯氧基亚胺型稀土金属催化剂、制备方法及应用
EP2506972A4 (fr) * 2009-12-03 2017-10-25 Materia, Inc. Catalyseurs supportés de métathèse d'oléfines
CN107501309A (zh) * 2017-09-01 2017-12-22 南京林业大学 一种希夫碱稀土镱碘化物及其制备方法和应用
EP2758413B1 (fr) * 2011-09-20 2018-03-07 Dow Corning Corporation Catalyseurs d'hydrosilylation contenant de l'iridium et compositions contenant les catalyseurs
CN109293706A (zh) * 2018-11-29 2019-02-01 上海应用技术大学 含铱氮双重键的三价铱亚胺配合物、制备方法及其应用
CN109651445A (zh) * 2019-01-22 2019-04-19 上海应用技术大学 一种大位阻三价铑亚胺配合物的制备及其应用
CN109896958A (zh) * 2017-12-07 2019-06-18 中国科学院大连化学物理研究所 一种1,2,4,5-环己烷四甲酸四乙酯的合成方法
WO2019138323A1 (fr) * 2018-01-09 2019-07-18 The Hong Kong Polytechnic University Composés présentant une activité antimicrobienne
CN111278559A (zh) * 2017-09-05 2020-06-12 Scg化学有限公司 适用于环酯和环酰胺的开环聚合的催化剂
CN112175122A (zh) * 2020-09-27 2021-01-05 中国科学院青岛生物能源与过程研究所 一种三齿水杨醛亚胺钛络合物的应用、聚共轭二烯及其制备方法和应用
CN113398995A (zh) * 2021-06-03 2021-09-17 西南林业大学 新型光催化剂1-(氨甲基)环己基乙酸缩水杨醛席夫碱-铜(ii)微晶的合成及应用
CN114591375A (zh) * 2022-03-23 2022-06-07 国科广化精细化工孵化器(南雄)有限公司 一种咪唑啉改性铁金属配合物及其制备方法与应用
CN115873221A (zh) * 2021-12-17 2023-03-31 浙江新和成股份有限公司 一种含磷聚合物及其制备方法和应用
CN116060010A (zh) * 2023-03-31 2023-05-05 北京宇极科技发展有限公司 引发剂、氟化催化剂以及e-1,1,1,4,4,4-六氟-2-丁烯的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010051268A1 (fr) 2008-10-31 2010-05-06 Dow Global Technologies Inc. Procédé de métathèse d'oléfines employant un complexe bimétallique du ruthénium avec des ligands pontants hydrido

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062253A1 (fr) * 2002-01-22 2003-07-31 Universiteit Gent Complexes metalliques a utiliser dans une metathese

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062253A1 (fr) * 2002-01-22 2003-07-31 Universiteit Gent Complexes metalliques a utiliser dans une metathese

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BRUNNER ET AL: "Sterochemistry and the chiral ruthenium atom in half-sandwich compounds.X-ray Structure analysis and appeal for the proper use of sterochemical terminology" INORG. CHEM., vol. 34, 1995, pages 3349-3351, XP002317378 *
BRUNNER ETAL: "Synthesis, properties, sterochemistry and crystal structures of diasteromric benzene-ruthenium(II) complexes with a chiral salicylideneaminato ligand" J. CHEM. SOC., DALTON TRANSACTIONS, 1996, pages 1499-1508, XP002317377 *
VERPOORT ET AL: "A new class or ruthenium complexes containing Schiff base ligands as promising catalysts for atom transfer radicla polymerisation and ring opening metathesis polymerization" JOURNAL OF MOLECULAR CATALYSIS A, vol. 180, 2002, pages 67-76, XP002317380 *
VERPOORT ET AL: "Easily accessible ring opening metathesis and atom transfer radical polymerization catalysts based on arene, norbornadiene and cyclooctadiene ruthenium complexes bearing Schiff base ligands" ADVANCED SYNTHESIS AND CATALYSIS, vol. 345, no. 3, March 2003 (2003-03), pages 393-401, XP002317376 *
VERPOORT ET AL: "Ring-closing metathesis, Kharasch addition and enol ester synthesis by a novel class of ruthenium (II) complexes" TETRAHEDRON LETTERS, vol. 42, 2001, pages 8959-8963, XP002317379 *

Cited By (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8415512B2 (en) 2001-06-20 2013-04-09 Grt, Inc. Hydrocarbon conversion process improvements
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7687635B2 (en) 2002-01-22 2010-03-30 Telene S.A.S. Metal complexes useful in metathesis and other reactions
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US8232441B2 (en) 2004-04-16 2012-07-31 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
WO2007022945A3 (fr) * 2005-08-22 2007-05-03 Viacatt N V Complexes metalliques a coordonnees multiples conçus pour etre utilises dans des metatheses
WO2007022945A2 (fr) * 2005-08-22 2007-03-01 Viacatt N.V. Complexes metalliques a coordonnees multiples conçus pour etre utilises dans des metatheses
US8927670B2 (en) 2005-08-22 2015-01-06 Rimtec Corporation Multicoordinated metal complexes for use in metathesis reactions
JP2009504401A (ja) * 2005-08-22 2009-02-05 テレーヌ ソシエテ パル アクシオン サンプリフィエー 転換反応に使用する多座配位金属錯体
EP1757613A1 (fr) * 2005-08-22 2007-02-28 Viacatt N.V. Complexes en métal multi coordonné pour l'usage dans des réactions de metathesis
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
CN100586966C (zh) * 2007-12-06 2010-02-03 中国科学院长春应用化学研究所 一种双水杨醛亚胺钒烯烃聚合催化剂及制备方法和应用
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
EP2506972A4 (fr) * 2009-12-03 2017-10-25 Materia, Inc. Catalyseurs supportés de métathèse d'oléfines
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
WO2012076542A1 (fr) * 2010-12-07 2012-06-14 Solvay Sa Polymérisation radicalaire régulée de monomères halogénés
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
EP2758413B1 (fr) * 2011-09-20 2018-03-07 Dow Corning Corporation Catalyseurs d'hydrosilylation contenant de l'iridium et compositions contenant les catalyseurs
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
WO2014139747A1 (fr) * 2013-03-13 2014-09-18 Evonik Industries Ag Génération in situ de catalyseurs au ruthénium pour la production d'oléfines par double décomposition
EP2778154A1 (fr) * 2013-03-13 2014-09-17 Evonik Industries AG Génération in situ de catalyseurs de ruthénium pour la métathèse d'oléfine
CN103949288A (zh) * 2014-04-10 2014-07-30 北京化工大学 分子筛负载的Cu-Co希夫碱配合物及其制备方法和应用
WO2016000242A1 (fr) 2014-07-03 2016-01-07 Guang Ming Innovation Company (Wuhan) Catalyseurs à base de métaux de transition du groupe 8 ainsi que leurs procédés de fabrication et leurs procédés d'utilisation dans la réaction de métathèse
RU2674471C2 (ru) * 2014-07-03 2018-12-11 Гуан Мин Инновейшн Компани (Ухань) Катализаторы на основе переходного металла 8 группы, способ их получения и способ их применения в реакции метатезиса
DE102015201292A1 (de) * 2015-01-26 2016-07-28 Henkel Ag & Co. Kgaa Organische Zinkkomplexe als Katalysatoren für Kondensationsreaktionen
CN106046207A (zh) * 2016-05-31 2016-10-26 北京理工大学 一种苯氧基亚胺型稀土金属催化剂、制备方法及应用
CN107501309B (zh) * 2017-09-01 2018-10-09 南京林业大学 一种希夫碱稀土镱碘化物及其制备方法和应用
CN107501309A (zh) * 2017-09-01 2017-12-22 南京林业大学 一种希夫碱稀土镱碘化物及其制备方法和应用
CN111278559A (zh) * 2017-09-05 2020-06-12 Scg化学有限公司 适用于环酯和环酰胺的开环聚合的催化剂
CN109896958A (zh) * 2017-12-07 2019-06-18 中国科学院大连化学物理研究所 一种1,2,4,5-环己烷四甲酸四乙酯的合成方法
CN109896958B (zh) * 2017-12-07 2021-06-01 中国科学院大连化学物理研究所 一种1,2,4,5-环己烷四甲酸四乙酯的合成方法
US11479529B2 (en) 2018-01-09 2022-10-25 The Hong Kong Polytechnic University Compounds with antimicrobial activity
JP7450887B2 (ja) 2018-01-09 2024-03-18 ザ ホンコン ポリテクニック ユニバーシティ 抗菌活性を備えた化合物
WO2019138323A1 (fr) * 2018-01-09 2019-07-18 The Hong Kong Polytechnic University Composés présentant une activité antimicrobienne
CN111971271A (zh) * 2018-01-09 2020-11-20 香港理工大学 一种具有抗菌活性的化合物
CN111971271B (zh) * 2018-01-09 2023-10-10 香港理工大学 一种具有抗菌活性的化合物
JP2021510143A (ja) * 2018-01-09 2021-04-15 ザ ホンコン ポリテクニック ユニバーシティ 抗菌活性を備えた化合物
CN109293706A (zh) * 2018-11-29 2019-02-01 上海应用技术大学 含铱氮双重键的三价铱亚胺配合物、制备方法及其应用
CN109651445A (zh) * 2019-01-22 2019-04-19 上海应用技术大学 一种大位阻三价铑亚胺配合物的制备及其应用
CN112175122B (zh) * 2020-09-27 2022-09-27 中国科学院青岛生物能源与过程研究所 一种三齿水杨醛亚胺钛络合物的应用、聚共轭二烯及其制备方法和应用
CN112175122A (zh) * 2020-09-27 2021-01-05 中国科学院青岛生物能源与过程研究所 一种三齿水杨醛亚胺钛络合物的应用、聚共轭二烯及其制备方法和应用
CN113398995A (zh) * 2021-06-03 2021-09-17 西南林业大学 新型光催化剂1-(氨甲基)环己基乙酸缩水杨醛席夫碱-铜(ii)微晶的合成及应用
CN113398995B (zh) * 2021-06-03 2023-08-15 西南林业大学 光催化剂1-(氨甲基)环己基乙酸缩水杨醛席夫碱-铜(ii)微晶的合成及应用
CN115873221A (zh) * 2021-12-17 2023-03-31 浙江新和成股份有限公司 一种含磷聚合物及其制备方法和应用
CN115873221B (zh) * 2021-12-17 2024-06-04 浙江新和成股份有限公司 一种含磷聚合物及其制备方法和应用
CN114591375A (zh) * 2022-03-23 2022-06-07 国科广化精细化工孵化器(南雄)有限公司 一种咪唑啉改性铁金属配合物及其制备方法与应用
CN116060010A (zh) * 2023-03-31 2023-05-05 北京宇极科技发展有限公司 引发剂、氟化催化剂以及e-1,1,1,4,4,4-六氟-2-丁烯的制备方法

Also Published As

Publication number Publication date
WO2005035121A3 (fr) 2005-06-30

Similar Documents

Publication Publication Date Title
WO2005035121A2 (fr) Complexes metallliques a base de schiff utilisables comme catalyseurs en synthese organique
EP1577282B1 (fr) Complexes de métaux pour utilisation dans la métathèse d'oléfines et les réactions à transfert d'atome ou de groupe
US7687635B2 (en) Metal complexes useful in metathesis and other reactions
US20070185343A1 (en) Metal complexes for use in olefin metathesis and atom group transfer reactions
Dorel et al. Photoswitchable catalysis based on the isomerisation of double bonds
JP4234636B2 (ja) 高メタセシス活性のルテニウムおよびオスミウム金属カルベン錯体
EP1056538B1 (fr) Activation par l'acide de catalyseurs de metathese a ruthenium et polymerisation vivante par metathese a ouverture de cycle (romp) dans l'eau
Gandelman et al. A new general method for the preparation of metal carbene complexes
Kanbayashi et al. Living cyclocopolymerization through alternating insertion of isocyanide and allene via controlling the reactivity of the propagation species: detailed mechanistic investigation
Izawa et al. (Arylimido) niobium (V)–Alkylidenes, Nb (CHSiMe3)(NAr)[OC (CF3) 3](PMe3) 2, That Enable to Proceed Living Metathesis Polymerization of Internal Alkynes
Segalovich-Gerendash et al. Ruthenium Olefin Metathesis Catalysts with Six-Membered Chelating Dithioacetal Ligands: Synthesis and Reactivity
Delfosse et al. Controlled radical polymerisation of vinyl monomers catalysed by ruthenium N-heterocyclic carbene complexes
Yazerski et al. Heterogenization of Homogeneous Catalysts on Dendrimers
Ralph Immobilization of homogeneous asymmetric hydrogenation catalysts by alternating ROMP assembly
Tancu Monofunctional and dendritic schiff base (N, N′) ruthenium carbene

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase