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  • 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
  • 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
• • 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
  • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
  • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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  • 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
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/28—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F132/02—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
  • C08F132/06—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
• • 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
• • 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
  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

• Novel ruthenium complexes their use in the metathesis reactions, and a process for carrying out the metathesis reaction
• the invention concerns novel metal complexes, their use as (pre)catalysts in the metathesis reaction as well as the process for carrying out the metathesis reaction.
• the third- generation catalysts initiate the metathesis reactions very promptly, whereas, in some metathesis applications, such as mould ROMP polymerisation, it is preferred to use a (pre)catalyst that does not initiate the reaction immediately after adding it to the substrate but only after an appropriate initiation by chemical agents, temperature or light.
• the complexes characterised by delayed initiation are often termed Anlagendormant catalysts" (Monsaert, S.; Vila, A. L.; Drozdzak, R.; Van Der Voort, P.; Verpoort, F., Chem. Soc. Rev., 2009, 38, 3360; R. Drozdzak, N. Nishioka, G. Recher, F. Verpoort, Macromol. Symp.
• Exemplary prisondormant catalysts are the complexes A-F, as well as the recently obtained P-l and P-2 (Pietraszuk, C; Rogalski, S.; Powala, B.; Montgomerykiewski, M.; Kubicki, M.; Spolnik, G.; Danikiewicz, W.; Wozniak, K.; Pazio, A.; Szadkowska, A.; Kozlowska, A.; Grela, K., Chem. Eur. J, 2012, 18, 6465-6469).
• the mould ROMP polymerisation allows obtaining finished articles.
• Dicyclopentadiene is one of the monomers frequently used for the mould polymerisation.
• the ruthenium complexes depicted by the formula 1 possessing in their structure a covalent metal-oxygen or metal-sulphur bond were very stable and might be prepared without any protective atmosphere of inert gas, as well as in the solvents of analytical grade (pro analyst).
• the complexes of the general formula 1 actively catalyse the metathesis reactions carried out in the presence of air.
• the complexes of the general formula 1 actively catalyse the metathesis reactions only after being activated by chemical agents, and they are very hardly susceptible to thermal activation.
• the complexes of the general formula 1 allowed obtaining polydicyclopentadiene via the ROMP-type reaction carried out in the air, the amount of the (pre)catalyst used being significantly lower than that in the case of using classical complexes.
• this amount of the (pre)catalyst is less than half of that in the case of the catalyst G (M. Perring, N.B. Bowden Langmuir, 2008, 24, 10480-10487).
• the (pre)catalyst according to the invention containing two phosphine ligands is more active in the ROMP reaction of polydicyclopentadiene than the structurally similar complex G'.
• the effect of an electron-acceptor substituent on the rate of initiation of a (pre)catalyst was reversed in the case of complexes of the general formula 1 compared to the case of the classical complex of the Hoveyda-Grubbs type (K. Grela, S.
• NHC N- heterocyclic carbene ligand
• the invention is related to the complexes of the general formula 1:
• X is an anionic ligand
• Y is oxygen or sulphur
• R1 is hydrogen, C ⁇ _20 alkyl, C2-20 alkenyl, C2-20 alkynyl or C5- I o aryl;
• R2 R3, R4 and R5 are independently hydrogen, halo, C1 -C1 alkyl, C1 -C1 alkoxy, Ci - C15 perfluoroalkyl, C3-C7 cycloalkyl, C2-C1 alkenyl, C5-C14 aryl, C5-C14 perfluoroaryl, C3-C12 heterocyclyl, -OR 6 , -N0 2 , -COOH, -COOR 6 , -CONR 6 R 7 , -S02NR 6 R 7 , -SO2R 6 , -CHO, -COR 6 , wherein R 6 and R 7 are independently Ci -C5 alkyl, C1 -C5 perfluoroalkyl, C5-C14 aryl, C5-C14 perfluoroaryl; R2 R3, R4 and R5 may be optionally joined together to form a substituted or unsubstituted, fused carbocyclic
• R 9 is of the formula PR 9 (R10)(R11) ; wherein R 9 , R1° and R 11 are independently Ci _i2 alkyl, C1.12 alkoxy, C3.12 cycloalkyl, C5.14 aryl, C5.14 aryloxy, C5.12 heterocyclyl; and two substituents from among R9, RIO and R 1 1 may additionally join together to form a cyclic system; or is an N-heterocyclic compound;
• the substituents R 1, R2 R3, R4 and R5 as well as Y are as defined above, and
• R ⁇ , RIO and RH are independently C1.12 alkyl, C1.12 alkoxy, C3.12 cycloalkyl, C5.14 aryl, C5.14 aryloxy, C5-I2 heterocyclyl; and two substituents from among R ⁇ , RIO and RH may additionally join together to form a cyclic system; or L 1 or are an N-heterocyclic compound selected from the group comprising: pyridine, 4-(N,N-dimethylamino)pyridine, 3-bromopyridine, piperidine, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, 1,2,3-triazole, 1,3,4- triazole, 1,2,3-triazine as well as 1,2,4-triazine.
• X is chloro
• Rl is hydrogen
• R 2 , R3, R4 and R5 are independently hydrogen or nitro
• Y is oxygen
• L 2 is a ligand of the formula 2a or 2b:
• Rl2 R13 are independently C1 -C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C14 aryl, optionally substituted with at least one of C1 -C5 alkyl, C1 -C5 perhaloalkyl, C1 -C5 alkoxy or halo;
• R 14 , R 15 , R 16 , R 17 are independently hydrogen, C1 -C12 alkyl, C3-C12 cycloalkyl, C2- C ⁇ 2 alkenyl, C5-C14 aryl, optionally substituted with at least one of C1 -C5 alkyl, C1 -C5 perhaloalkyl, Ci -C5 alkoxy or halo, and R 14 Rl5, Rl6, R17 may optionally join together to form a substituted or unsubstituted, fused carbocyclic ring C4_g, or a substituted or unsubstituted, fused aromatic ring.
• X is chloro
• Rl is hydrogen
• R 2 , R3, R4 and R5 are independently hydrogen or nitro
• Y is oxygen
• L2 is a SIMes or SIPr ligand:
• the invention is related also to use of the complexes of the general formula 1, wherein all substituents are as defined in claim 1, as (pre)catalysts in the metathesis reactions.
• the complexes of the general formula 1 are used as (pre)catalysts in the reactions of ring-closing metathesis, cross metathesis, homometathesis, alkene-alkyne type metathesis; more preferably, the complexes of the general formula 1 are used as (pre)catalysts in the reaction of ring-opening metathetic polymerisation.
• the invention concerns also a process for carrying out the metathesis reaction of olefins, wherein at least one olefin is contacted with a complex of the general formula 1 as a (pre)catalyst.
• the metathesis reaction is carried out in an organic solvent; more preferably, the organic solvent is dichloromethane, dichloroethane, toluene, ethyl acetate.
• the metathesis reaction is carried out without any solvent.
• the metathesis reaction is carried out in the presence of a chemical activator; more preferably, the chemical activator is a Br0nsted or Lewis acid or a halo-derivative of alkane or silane; most preferably, the activator is hydrogen chloride, chlorotrimethylsilane or /7-toluenesulphonic acid.
• a chemical activator is a Br0nsted or Lewis acid or a halo-derivative of alkane or silane; most preferably, the activator is hydrogen chloride, chlorotrimethylsilane or /7-toluenesulphonic acid.
• the metathesis reaction is a ring-opening metathetic polymerisation of dicyclopentadiene .
• the (pre)catalyst of the general formula 1 is added in the solid form to dicyclopentadiene .
• the polymerisation reaction is initiated by heating the mixture of dicyclopentadiene and the (pre)catalyst of the general formula 1 to a temperature of 30°C or higher.
• the starting material contains at least 94 wt. of dicyclopentadiene.
• the metathesis reaction is carried out at a temperature of from 20 to 120°C.
• the metathesis reaction is carried out in a period of from 1 minute to 24 hours.
• the metathesis reaction is carried out in the presence of an additive promoting formation of cross bonds.
• the metathesis reaction is carried out using the amount of the (pre)catalyst equal to or less than 1000 ppm.
• thetician(pre)catalyst term is used to indicate that the complex according to the invention may be either the catalyst itself or a precursor of the active species being the actual catalyst.
• the term corpus represents an element selected from F, CI, Br, I.
• the termticianalkyl concerns a saturated, straight-chain or branched-chain hydrocarbon substituent having the specified number of carbon atoms.
• alkyls are: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, ie/t-butyl, pentyl.
• the term unfoldingperfluoroalkyl represents the alkyl, as defined above, wherein all hydrogens have been replaced with halogen atoms, where the halogen atoms may be identical or different.
• the term “humancycloalkyl” concerns a saturated mono- or polycyclic hydrocarbon substituent having the specified number of carbon atoms.
• the non-limiting examples of a cycloalkyl substituent are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
• the term “suitalkenyl” concerns a non-cyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond.
• alkenyls are: vinyl, allyl, 1-butenyl, 2-butenyl.
• aryl concerns an aromatic mono- or polycyclic hydrocarbon substituent having the specified number of carbon atoms.
• aryl are: phenyl, mesityl, anthracenyl.
• the term “humanocyclyl” concerns aromatic as well as non-aromatic cyclic substituents having the specified number of carbon atoms, wherein one or more carbon atoms have been replaced with a heteroatom such as nitrogen, phosphorus, sulphur, oxygen, provided that there are no two directly connected oxygen or sulphur atoms in the ring.
• Non-aromatic heterocyclyls can contain from 4 to 10 atoms in the ring, whereas aromatic heterocyclyls must have at least 5 atoms in the ring.
• the benzo-fused systems also belong to heterocyclyls.
• non-aromatic heterocyclyls are: pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, dihydropyranyl, tetrahydrothiopyranyl, piperidinyl, morpholinyl, thiomorpholinyl, 2-pyrrolinyl, indolinyl.
• aromatic heterocyclyls are: pyridinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, furyl, thienyl.
• the above-mentioned groups may be bound via a carbon atom or a nitrogen atom.
• the substituent obtained by binding pyrrole may be either pyrrol- 1-yl (N-bound) or pyrrol-3-yl (C-bound).
• the term charged ligand concerns a substituent having no electrical charge, capable of coordinating to a ruthenium atom.
• the non-limiting examples of such ligands are: N- heterocyclic carbene ligands, amines, imines, phosphines and oxides thereof, alkyl and aryl phosphites and phosphates, ethers, alkyl and aryl sulphides, co-ordinated hydrocarbons, haloalkanes and haloarenes.
• the term termed neutral ligand encompasses also N-heterocyclic compounds; their non-limiting examples are: pyridine, 4-(N,N-dimethylamino)pyridine (DMAP), 3-bromopyridine, piperidine, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, 1,2,3-triazole, 1,3,4-triazole, 1,2,3-triazine and 1,2,4-triazine.
• DMAP N,N-dimethylamino)pyridine
• the neutral ligands and may be bound with the benzylidene ligand, as well as they may be bound together to form a bidentate ligand (L ⁇ -L ⁇ ); moreover, the neutral ligands may be bound to an anionic ligand X to form multidentate ligands.
• the term termed herein concerns the substituent capable to co-ordination with a metal centre, bearing an electrical charge capable to compensate the charge of the metal centre, wherein such a compensation may be complete or partial.
• anionic ligands are: fluoride, chloride, bromide or iodide anions, carboxylic acid anions, alcohol and phenol anions, thiol and thiophenol anions, (organo)sulphuric and (organo)phosphoric acid anions as well as anions of esters thereof.
• the anionic ligand (X) and the neutral ligands (L ⁇ , L ⁇ ) may be bound together, resulting in formation of multidentate ligands.
• multidentate ligands are: a bidentate ligand ( ⁇ -Ll), a tridentate ligand (Xl-L ⁇ -L ⁇ ).
• ligands are: anion of 2-hydroxyacetophenone, anion of acetylacetone.
• the term tugcarbene concerns a molecule containing a neutral carbon atom having the valence number of 2 and two non-paired valence electrons.
• the term perhapscarbene encompasses also carbene analogues, wherein the carbon atom is replaced with another chemical element such as: boron, silicon, nitrogen, phosphorus, sulphur.
• the term perhapscarbene relates particularly to N-heterocyclic carbene (NHC) ligands.
• NHC N-heterocyclic carbene
• non-limiting examples of preferred agents promoting formation of cross bonds are iert-butyl peroxide, di-iert-butyl peroxide, and also mixtures thereof.
• the solid carbene complex 4 (100 mg, 0.115 mmol) was placed in a Schlenk flask, this was followed by adding anhydrous, deoxygenated methylene chloride (7 ml) and anhydrous pyridine (93 ⁇ , 1.15 mmol). The resulting solution was stirred at a temperature of 40°C for 24 hours. The reaction mixture was introduced at the top of a chromatographic column packed with silica gel. Since that moment, all subsequent operations were carried out in the air, with no need for using the protective argon atmosphere. The column was eluted using a solution of ethyl acetate - cyclohexane (0 to 10 vol.%). After evaporating the solvents, the complex 5 was obtained as a brown solid (42 mg, 54% yield).
• the complex 6 was prepared according to the method described for the complex 3 (in Example 4), to obtain the product as a green solid in 70% yield.
• Dicyclopentadiene (1 g, 7.56 mmol) was charged into the polymerisation vial, in the air, and, after melting, it was placed in an oil bath at a temperature of 28°C. Then appropriate amounts of the (pre)catalyst (as a solid in experiments 2, 3, 6-11, or as a solution in a minimum amount of dichloromethane) as well as of the chemical activator (4 equivalents with relation to the (pre)catalyst; no activator was added in the case of experiments 1-3) were added, and the vial was transferred to a bath at an appropriate temperature (as indicated in the table below) and kept for an appropriate period of time (as indicated in the table below).
• Dicyclopentadiene (10 g, 76 mmol) was charged into the polymerisation vial, in the air, and, after melting, it was placed in an oil bath at a temperature of 28 °C. Then the (pre)catalyst 4 (as a solution in a minimum amount of dichloromethane) was added and the vial was kept in a bath at a temperature of 28 °C for 24 h. No substrate conversion was observed (the vial contained liquid monomer only).
• the complexes of the general formula 1 according to the invention promote the olefin metathesis reactions effectively, following chemical activation.
• the complexes 3 and 4 demonstrate a very high effectiveness in the ring-opening polymerisation (ROMP) of dicyclopentadiene.
• the initiation of the polymerisation reaction may be controlled to a very high degree due to delayed initiation characterising the complexes of the general formula 1.
• the state of the art complexes of the formulae D and D' exhibit similar properties and effectiveness, as results from the literature data.
• complexes of the general formula 1 are synthesized by using the appropriate thallium derivatives what presents the health concerns (thallium compounds used in the synthesis are very toxic) as well as lengthens and complicates the synthesis of such complexes.
• the properties of the complexes of the general formula 1 may be significantly altered by the choice of appropriate ligands.
• the high stability of the complexes of the general formula 1 allows for carrying out the polymerisation process in the presence of oxygen; because of that, there is no need for deoxygenating the commercially available dicyclopentadiene and also it is not necessary to use an inert gas atmosphere during the process itself. It is unexpectedly found that the course of the polymerisation reaction (the form of the polymer) may be controlled by the choice of the activating agent.

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