GB2447068A - Catalytic olefin metathesis reaction method - Google Patents

Catalytic olefin metathesis reaction method Download PDF

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GB2447068A
GB2447068A GB0703509A GB0703509A GB2447068A GB 2447068 A GB2447068 A GB 2447068A GB 0703509 A GB0703509 A GB 0703509A GB 0703509 A GB0703509 A GB 0703509A GB 2447068 A GB2447068 A GB 2447068A
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catalyst system
groups
group
reactions
formula
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Michael Green
Duncan Frank Wass
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University of Bristol
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University of Bristol
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Abstract

A method for performing an olefin metathesis or cross-coupling reaction is characterised by the catalyst system comprising: [a] a source of a d-block metal, such as Group VIII metal, iron, cobalt, copper, ruthenium, rhodium, nickel, palladium or platinum [b] optionally a promoter, an activator and/or a base, and [c] a source of a 3-membered carbocyclic ligand. Also disclosed is catalysing olefin metathesis or cross-coupling reactions, comprising the catalyst system and a method of producing the catalyst system wherein [b] optionally a promoter, an activator and/or a base is a further reagent.

Description

CATALYTIC METHOD
The present invention relates to methods fpr performing olefin metathesis or cross-coupling reactions in the presence of a catalyst system, catalyst systems for use in the methods, processes for preparation of the catalyst systems and uses of the catalyst systems in the methods.
Complexes of transition metals have found widespread use as homogeneous catalysts (Applied Homogeneous Catalysis with Organometallic Compounds, Cornils, B.; Herrmann, W.A. (Eds), VCH Weinheim, 1996, 258). They are particularly useful for catalytic reactions involving the formation of carbon-carbon or carbon-heteroatom (for example, H, N, 0, P) bonds, two important classes of reaction being so-called cross-coupling' reactions (Metal Catalyzed Cross-Coupllng Reactions, 2 ed, de Meijere and Diederich (eds), Wiley-VCH, 2004) and metathesis' reactions (also known as olefin metathesis reactions) (Handbook of Metathesis, Grubbs (ed) Wiley-VCH, 2003).
A crucial consideration in these applications is the supporting ligands around the transftion metal centre, modification of which can lead to industrially useful benefits such as improved stability, selectivity and activity.
A number of such supporting ligands have been disclosed, often based on N-or P-donor sets. More recently, ligands based on cyclic hetercatom-stabilised C-donors have also been described, such ligands often being called N-heterocyclic carbenes (W A. Herrmann, C KOcher, Angewandte Chemie International Edition, 1997, 36, 2162-2187) and, even more recently, carbocyclic (i.e. no heteroatom) carbene ligands based on 7-membered rings have been disclosed (W.A. Herrmann et al, Angewandte Chemie International Edition, 2006, 45, 3859-3862).
Metal complexes supported by 3-membered carbocyclic ring ligands are known. A particular palladium complex with a cyclopropene ligand has been shown to catalyse an isomerisation reaction as disclosed in EP-A- 0118801 and Yoshida et al Tetrahedron 44, (1988) p55.
Other complexes based on cyclopropene have also been disclosed in Yoshida etal: Chemist,yLetters, 1978, 241 and 1341; J. Phys. Org. Chem., 1988, 332; Ofele, Angewante C/iemie. mt. Ed. 1968, 7, 950 (Cr); Schubert et al; J Am. Chem. Soc., 1991, 113, 2228 and Organometallics, 1988, 7, 784 (Mn).
However, use of these complexes as catalysts for reactions involving the formation of carbon-carbon or carbon-heteroatom bonds has not been disclosed.
We have found that, surprisingly, metal complexes with a 3-membered carbocyclic ring ligand are very efficient catalysts for such reactions and, moreover, show improved catalytic activity compared to other systems The present invention accordingly provides a method for performing an olefin metathesis or a cross-coupling reaction, characterised in that the method is performed in the presence of a catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand.
The d-block metal is preferably a Group VIII metal (referring to Chemical Abstracts Service group notation, 1986; Group VIII metals correspond to IUPAC recommended notation for Groups 8, 9 and 10 of the Periodic Table: the Fe, Co and Ni groups) or Cu, more preferably a Group VIII metal, and most preferably Ru, Rh, Ni, Pd or Pt. Preferably, the 3-membered carbocyclic ligand comprises a group of formula wherein (i) R1 and R2 are independently selected from hydrocarbyl or heterohydrocarbyl groups, or (ii) R and R2, together with the carbons to which they are attached, form a five, six, seven or eight membered ring.
The broken line in the formula of the carbocyclic ligand indicates the bond to the d-block metal.
Suitable hydrocarbyi groups are alkyl, for example methyl, ethyl, n-propyl, isopropyl, t-butyl, adamantyl; aryl or substituted aryl, for example phenyl, ortho-tolyl, meta-tolyl, para-tolyl, ethylphenyl, isopropylphenyl, t- butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, naphthyl, benzyl, alkenyl or alkynl groups. Suitable heterohydrocarbyl groups may have one or more heteroatorns and this may be attached directly to the 3-membered ring or at any other substituent position on the group. Suitable examples where the heteroatom is attached directly to the 3-membered nng are: -Z(R3)ITlwhereZisSiandrnis3,ZisNandmls2,zispandmjs2z is 0 and m is 1, or Z is S and m is 1; the groups R are the same or different hydrocarbyl groups as defined above.
Suitable examples where the heteroatom(s) are in other positions are: CF3, CF2CF3, CH2OMe, CH2NMe2, CH2CH2NH2, CH2CH2N(R52, CH2CH2P(R1)2, CH2CH2CH2F(R)2, fluorophenyl, perfluorophenyl, chiorophenyl, bromophenyl, C6H4(CF3), C6H3(CF3)2, C6H4(OMe), C6H3(OMe)2, C6H4(N(R')2), C6H4(P(R1)2), where R' is as defined above.
For some values of Rt and R2, these groups may themselves act as supporting ligands to the metal, for example when R' is CH2CH2P(R')2 the P-atom of this group may donate to the metal as a phosphine donor ligand. In this alternative, R1 andlor P2 are such that the 3-membered carbocyclic ligand is a multidentate ligand P and R', together with the carbons of the 3-membered ring to which they are attached, may form a five, six, seven or eight membered ring so that the ligand has a bicyclic structure.
The catalyst system may be formed in situ during the reaction or the catalyst system may be pre-formed.
If the catalysts system is pre-formed, the catalyst system may, preferably, comprise a compound of formula M ( L) wherein M is a d-block metal, n is 0 to 5 and the L groups, which may be the same or different, are ligands.
The L groups may be the same or different and are either additional ligands needed to stabilise the overall complex, for example, chloride, bromide, iodide, hydride, alkoxide, amide, acetate, acetylacetonate, amine, ether, water, phosphines such as triphenylphosphine or triphenoxyphosphine, pyridine, alkenes, alkynes, N-heterocyclic carbenes, etc; or reactive ligands that can be the active site of the catalysts, for example alkyl, aryl, carbene, alkylidene. Some of the L groups described as stabilising groups can also be reactive ligands in some circumstances, for example amide and hydride. L may also be a substrate molecule for the catalytic reaction being performed.
L may be a 3-membered carbocyclic ring ligand as defined above, giving an overall structure of: in the case where one L group is an additional 3-membered carbocyclic ring.
The value of n will vary depending on the nature of L and the required valericy of M but will generaily be between 0 and 5.
The olefin metathesis reaction may be selected from cross-metathesis, ring closing metathesis, enyne metathesis, ring opening metathesis, ring opening metathesis polymensation, acyclic diene metathesis or alkyne metathesis.
The cross-coupling reaction may be selected from 1) Cross-coupling reactions with organoboron compounds, for example Suzuki coupling, 2) Cross-coupling reactions with organotin compounds for example Stille coupling, 3) Cross-coupling reactions with organozinc compounds, 4) Cross-coupling reactions with organomagnesium compounds, 5) Crosscoupling reactions with other organometallic compounds, for example Negishi coupling, 6) Cross-coupling reacations with allylic compounds, 7) Cross-coupling reactions with conjugated diene compounds, 8) Carbometallation reactions, 9) Cross-coupling reactions with alkyne compounds, for example Sonogashira reaction, 10) Cross-coupling reactions with olefinic compounds, for example Heck reaction, 11) Cross-coupling reactions involving a cyclometallation step, 12) Cross-coupling reactions for the formation of carbon-heteroatom bonds (e.g. C-N, C-O), for example Buchwald-Hartwig reactions The detairs of such reactions are wefl-known to the skilled person as described in, for example, "Metal Catalysed Cross-coupling Reactions" 2 edition, edited by de Meijere and Diederich, Wiley-VCH 2004.
Catalytic reactions may be carried out on a wide variety of substrates including those that have been previously disclosed for cross coupling or metathesis catalysis and at temperatures between -100 C and 250 C, preferably between 0 C and 200 C. Reactions are typically carried out in a solvent diluent, although the substrates or reaction products themselves may also be used as solvents. The solvent diluent of choice will depend on the solubility characteristics of the specific catalysts and substrates used and a wide variety of suitable solvents are suitable, including hydrocarbons (e.g. (-) alkanes, benzene, toluene, xylene) and polar solvents (e.g. ethers, halocarbons, acetone, DMA, DMF, DMSO, MeCN etc.). Alternatively, the catalyst may be in the solid phase by heterogenisation on a suitable carrier such as a polymer, silica, carbon, alumina, etc For cross coupling catalysis, it is usually required to add a catalyst promoter, in excess, stoichiometric or sub-stoichiometric amounts to the substrates used. This promoter is usually a suitable base, such as an amine, amide, alkoxides, hydroxide, carbonate, phosphate or similar. Other possible promoters include halide ions. For metathesis catalysis, a promoter is usually not required, although in some specific cases one may be required to generate an active system.
In a second aspect, the present invention provides a catalyst system for catalysing olefin metathesis or cross-coupling reactions, the catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand Optional and/or preferred features of the catalyst system are generally as described above in relation to the first aspect of the invention.
Catalyst systems may be either pre-formed or formed in situ by mixing the component parts of the catalyst. Even in cases where a pre-formed catalyst system in the form of a discrete metal-ligand complex is used, this will often undergo further reaction during a catalytic run, resulting in a new complex in which the groups L have been removed, replaced or transformed into new L groups. Pre-formed catalyst systems may be made by those p skilled in the art by reaction of a transition metal source, a source of a 3 membered carbocyclic ligand and, optionally, a further reagent such as a base (for example: amines, amides, alkoxides, hydroxides, carbonates, BuLi or similar reagents), an acid, a reducing agent, an oxidising agent, or further group as defined as L above (or a source of a further group as defined as L).
Thus, in a third aspect, the present invention provides a method for producing a catalyst system for catalysing olefin metathesis or cross-coupling reactions, the method comprising combining a) a source of a d-block metal, b) optionally, a further reagent, c) a source of a 3-membered carbocyclic ligand.
Suitable sources of a transition metal are the metal itself, the metal dispersed on a suitable carrier material (for example silica or carbon) or a metal complex of formula ML1, where M and L are as defined above, and the value of m will vary depending on the nature of L and the required valency of M but will generally be between 1 and 6.
Suitable sources of a 3-membered carbocyclic ligand include the free carbene ligand: Such ligands are often unstable in their free form, and another suitable 3-rnembered carbocyclic ligand source is where the ligand has been stabilized by co-ordination to a Lewis acid fragment, as illustrated: :z where Z is a suitable Lewis acid, for example a main group Lewis acid such as a borane (eg. BH3, BCI3, BL3 and the like), appropriate group 13 compounds (e.g. AId3), appropriate group 14 compounds, (e.g. stannanes, SnCl2, SnCI4 and the like), appropriate group 15 compounds (e.g. SbF), or a further transition metal compound MLrn, as defined above.
S
Other suitable sources of a 3-membered carbocyclic ligand are substituted 3,3'-cyclopropene compounds as illustrated: where the X groups may be the same or different and may be a halide (F, Cl, Br, I, etc), pseudo-halide (e.g. N3, CN, NCO, OCN, etc.) or weakly-coordinating anion (eg. BF4, PF6, dO4, AsF6, Aid4, B(C6F5)4, etc), H, a main group metal or main group metal fragment (eg. Li, Na, K, MgCl) or transition metal fragment MLm as defined above.
The reagents may be combined in order to synthesise a pre-formed catalyst in a number of ways; for example: oxidative addition reaction of a low oxidation state metal source (eg. Pd metal, [Pd(PPh3)4, {RhCl(PPh3)3], [Ni(CO)4], etc) with a 3,3-dihalocyclopropene compound or analogous pseudo-halide or weakly-coordinating anion compound; reaction of a metal source with the free carbene; reaction of a metal source with 3,3'- dihalocyclopropene compound or analogous pseudo-halide or weakly-coordinating anion compound in the presence of a suitable reducing agent; reaction of a metal source with the free carbene; reaction of a metal source with the Lewis acid-protected carbene; reaction of a metal source with 3- halocyclopropene compound or analogous pseudo-halide or weakly-coordinating anion compound in the presence of a suitable base.
Subsequent modification of the complex to make other preformed catalysts with different L groups can be achieved by standard methods of ligand substitution, addition and/or removal.
Catalysts may also be formed in situ during a catalytic reaction, by addition of the various components as described above either in the presence or absence of the substrates to be converted during catalysis without isolating a discrete metal-ligand complex, although it is likely that similar complexes to those made using a the pre-formed method with be generated.
In this specification, for clarity, the bonding between the 3-membered carbocyclic ligand and the d block metal has been illustrated as This is only one of a number of resonance forms for this fragment having the same overall formula that could reasonably be drawn by those skilled in the art, and the description is not limited to this specific representation. The resonance form giving most accurate representation of this fragment is likely to vary between specific compounds and will depend on the other groups bonding to the 3-membered carbocycle.
In this specification, unless otherwise specified, "hydrocarbyl" refers to an optionally substituted hydrocarbon group and includes alkyl, alkenyl, alkynyl, 5-or 6-membered rings (that may be alicyclic or aryl and includes monocyclic, bicyclic or polycyclic fused ring systems), preferably C to C32, more preferably C to C24, most preferably C to C18 "Heterohydrocarbyl" refers to a group as defined above for hydrocarbyl but containing one or more heteroatoms preferably selected from Si, F, N, 0, S and F. Alkyl is preferably C1 to C6, more preferably straight chain C to C6 in particular methyl, ethyl, n-propyl or n-butyl The invention is illustrated by the Figure which is a single crystal X-ray diffraction structure of the compound described in Example 2.
The invention is further illustrated by the following Examples in which all procedures were carried out under an inert (N2) atmosphere using standard Schlertk line techniques or in an inert atmosphere (Ar) glovebox.
Chemicals were obtained from Sigma Aldrich and used without further purification unless otherwise stated.
Example 1. Synthesis of 1,2-diphenyl-3,3-dichlorocyclopropene I Diphenylcyclopropenone (1.00 g, 4.85 mmol) was heated at 40 C for 2 h in 2 ml of thionyl chloride The volatiles were removed in vacua to give a beige powder. The solid was dissolved in 6 ml of cyclohexane with heating and placed in a freezer overnight to give I.2-diphenyl-3,3-dichlorocyclopropene as pale yellow crystals in 59 % yield (0.75 g, 2 88 mmol).
Example 2. Synthesis of palladium complex 2 /C Ph3P CI 1,2-diphenyl-3,3-dichlorocyclopropene (47 mg, 0.18 mmol) and tctrokis(triphenylphosphne)pallad;um(0) (208 rig, 0.18 mmoi) were weighed into a Schlenk flask. 10 ml of toluene was added to give a yellow solution and a colourless precipitate immediately The mixture was stirred overnight The precipitate was collected by filtration and dried in vacua to give the illustrated compound 2 as a white solid in 50% yield. The product 2 can be recrystallised from CHCI3.
Charabteristic data: 31P{1H} NMR (121 MHz, CDCI3): O = 27.6, 1H NMR (400 MHz, CDCI3): 6 = 8.03 (m, 4H), 7.64 (m, 8H), 7.53 (m, 4H), 7.25 (m, 3H), 7.15 (it, 6H).
A single crystal X-ray diffraction structure of this compound was obtained and is shown in the Figure with significant bond lengths and angles in Table 1. In the Figure, hydrogen atoms are omitted for clarity. 1]
Table 1. Bond lengths (A) and angles ( ) Pdi-P1 2243 -.____ Pdi-Cll 2.362 Pdi-CI2 2.345 _______ 1.938 - C1-C2 -1.390 ____- C1-C3________ 1.387 - 2-C3 _____ 1.363 ____ LC2C1C3 59 ______ LIcic2c3 61 _____ f1Pd1C1______ 92 ____ Cli PdlCl2 ___ 93 Catalytic Experiments (see Table 2):
Examples 3-11
The same basic method was adopted for all of these examples for the illustrated reaction.
r,BuO RX _.? nBuO' R A Schlenk flask was charged with base as indicated in Table 2 (3.0 mmol), the aryl halide as indicated in Table 2 (2.0 mmol) and the internal standard diethylene glycol di-n-butyl ether (100mg). Then n-butyl acrylate (3 mmol) and degassed N,N- dimethylacetamide (DMA) (2 ml) were added and the reaction heated to 145 C. When the reaction had reached temperature, the required amount of catalyst 2 was added and the reaction stirred for the required run time. At the end of the reaction, the reaction mixture was allowed to cool, washed with dilute HCI (aq), extracted with dichioromethane and the organic phase dried over MgSO4. Conversion and yield was determined by GC relative to the internal standard. lfl 14.
Examples 12-16
Ph-B(OH)2 + R 2 Essentially the same method was used as described above, only n-butyl acrylate was replaced with phenylboronic acid, DMA was replaced with xylene and the reaction temperature was 130 00
Table 2:
Example R X Base Mol % Pd Conversion TON 3 C(O)Me Br NaOAc 0.0k 1 00 10 000 4 C(O)Me Hr NaOAc 10" 99 99 000 C(O)Me Br NaOAc I 0 94 940 000 6 H Br NaOAc 1 0 80 80 000 7 OMe Br NaOAe 10" 54 54000 8 C(O)Me CI NaOAc 1 98 98 9 C(O)Me Cl K2C01 1 100 100 C(O)Me (1 KC04 I 0 3 I 310 000 11 H Br K3C03 1 96 96 12 II Br Cs'C01 1 99 99 13 OMe Br KCO 1 97 97 14 C(O)Me Br K2CO 1 100 tOO C(O)Me Cl I i4 14 16 OMe Cl K2C03 1 6 6

Claims (46)

  1. A method for performing an olefin metathesis or a cross-coupling reaction, characterised in that the method is performed in the presence of a catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand.
  2. 2. A method as claimed in claim 1, wherein the d-block metal is a Group VIII metal or Cu.
  3. 3 A method as claimed in claim 2, wherein the d-block metal is selected from Ru, Rh, Ni, Pd or Pt.
  4. 4. A method as claimed in any one of the preceding claims, wherein the 3-membered carbocyclic ligand comprises a group of formula wherein (i) R' and R2 are independently selected from hydrocarbyl or heterohydrocarbyl groups, or (ii) R1 and R', together with the carbons to which they are attached, form a five, six, seven or eight membered ring.
  5. A method as claimed in claim 4, wherein the hydrocarbyl groups are selected from alkyl, aryl, alkenyl or alkynyl groups.
  6. 6. A method as claimed in claim 5, wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, t-butyl and adamantyl.
  7. 7. A method as claimed in claim 5, wherein the aryl group is selected from phenyl, ortho-tolyl, meta-tolyl, para-tolyl, ethyiphenyl, isopropylphenyl, t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5- dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropyiphenyl, naphthyl and benzyl.
  8. 8 A method as claimed in claim 4, wherein at least one heterohydrocarbyl group is attached directly to the 3-membered ring.
  9. 9. A method as claimed in claim 8, wherein the heterohydrocarbyl group is of formula -Z(R3). wherein Z is selected from Si, N, P, 0 or 5, m is 1 to 4, and wherein the groups R3 may be the same or different and each is a hydrocarbyl group.
  10. 10. A method as claimed in claim 4, wherein at least one heterohydrocarbyl group is not attached directly to the 3-membered ring.
  11. 11. A method as claimed in claim 10, wherein at least one heterohydrocarbyl group is selected from CF3, CF2CF3, CH2OMe, CH2NMe2, CH2CH2NH2, CH2CH2N(R1)2, CH2CH2P(R1)2, CH2CH2CH2P(R1)2, fluorophenyl, perfluorophenyl, chlorophenyl, bromophenyl, C6H4(CF3), C6H3(CF3)2, C6H4(OMe), C5H3(OMe)2, C6H4(N(R1)2), C6H4(P(R1)2), where R1 is as defined in claim 4.
  12. 12. A method as claimed in claim 4, wherein R' and/or R2 are such that the 3-membered carbocyclic ligand is a multidentate ligand.
  13. 13. A method as claimed in claim 12, wherein R and/or R' are of formula CH2CH2P(R)L wherein R is a hydrocarbyl group.
  14. 14. A method as claimed in any one of the preceding claims, wherein the catalyst system is formed in situ during the reaction.
  15. 15. A method as claimed in any one of claims ito 13, wherein the catalyst system is pre-formed.
  16. 16. A method as claimed in claim 15, wherein the catalyst system comprises a compound of formula wherein M is a d-block metal, n is 0 to 5 and the L groups, which may be the same or different, are ligands.
  17. 17. A method as ciaimed in ciaim i6, wrierein the L groups are stabilising ligands selected from chloride, bromide, iodide, hydride, alkoxide, amide, acetate, acetylacetonate, amine, ether, water, phosphines, pyridine, alkene, alkyne and N-heterocyclic carbenes.
  18. 18. A method as claimed in claim 16, wherein the L groups are reactive ligands selected from alkyl, aryl, carbene, alkylidene.
  19. 19. A method as claimed in claim 16, wherein at least one L is a substrate molecule for the reaction.
  20. 20. A method as claimed in claim 16, wherein at least one L is a 3-membered carbocyclic ligand, giving a compound of formula M(L wherein the L groups which may be the same or different, are ligands, p is 0 to 5, and R4 and R are as defined for R1 and R2 in ciaim 4.
  21. 21. A method as claimed in any one of the preceding claims, wherein the olefin metathesis reaction is selected from cross-metathesis, nng closing metathesis, enzyme metathesis, ring opening metathesis, ring opening metathesis polymerisation, acyclic diene metathesis or alkyne metathesis.
  22. 22. A method as claimed in any one of claims 1 to 20, wherein the cross-coupling reaction is selected from reactions with organoboron compounds, reactions with organotin compounds, reactions with organozinc compounds, reactions with organomagnesium compounds, reactions with other organometallic compounds, reactions with allylic compounds, reactions with conjugated diene compounds, carbometallation reactions, reactions with alkyne compounds, reactions with olefinic compounds, reactions involving a cyclometallation step and reactions for the formation of carbonheteroatom bonds.
  23. 23. A catalyst system for catalysing olefin metathesis or cross-coupling reactions, the catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand.
  24. 24. A catalyst system as claimed in claim 23, wherein the d-block metal is a Group VIII metal or Cu.
  25. 25. A catalyst system as claimed in claim 24, wherein the d-block metal is selected from Ru, Rh, Ni, Pd or Pt.
  26. 26. A catalyst system as claimed in any one of claims 23 to 25, wherein the 3-membered carbocyclic Iigand comprises a group of formula : wherein (i) R and R are independently selected from hydrocarbyl or heterohydrocarbyl groups, or (ii) R' and R2, together with the carbons to which they are attached, form a five, six, seven or eight membered ring.
  27. 27. A catalyst system as ciaimed in claim 26, wherein the hydrocarbyl groups are selected from alkyl, aryl, alkenyl or alkynyl groups.
  28. 28. A catalyst system as claimed in claim 27, wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, t-butyl and adamantyl.
  29. 29. A catalyst system as claimed in claim 27, wherein the aryl group is selected from phenyl, ortho-tolyl, meta-tolyl, para-tolyl, ethyl phenyl, isopropylphenyl, t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, naphthyl and benzyl.
  30. 30. A catalyst system as claimed in claim 26, wherein at least one heterohydrocarbyl group is attached directly to the 3-membered ring.
  31. 31. A catalyst system as claimed in claim 30, wherein the heterohydrocarbyl group is of formula -Z(R3)rn wherein Z is selected from Si, N, F, 0 or S and M is I to 4, and wherein the groups may be the same or different and each is a hydrocarbyl group.
  32. 32. A catalyst system as claimed in claim 26, wherein at least one heterohydrocarbyl group is not attached directly to the 3-membered ring.
  33. 33. A catalyst system as claimed in claim 32, wherein at least one heterohydrocarbyl group is selected from CF3, CF2CF3, CH2OMe, CH2NMe2, CH2CH2NH2, CH2CH2N(R1)2, CH2CH2P(R1)2 CH2CH2CH2P(R1)2, fluorophenyl, perfluorophenyl, chlorophenyl, bromophenyl, C6H4(CF3), C6H3(CF3)2, C5H4(OMe), C5H3(OMe)2, C5H4(N(R1)2), C6H4(P(R1)2), where R1 is as defined in claim 4.
  34. 34. A catalyst system as claimed in claim 26, wherein R and/or R2 are such that the 3-membered carbocyclic ligand is a multidentate ligand.
  35. A catalyst system as claimed in claim 34, wherein R' and/or R2 are of formula CH2CH2P(R)2 wherein R is a hydrocarbyl group.
  36. 36. A catalyst system as claimed in any one of claims 23 to 35, wherein the catalyst system comprises a compound of formula wherein M is a d-block metal, n is 0 to 5 and the L groups, which may be the same or different, are ligands.
  37. 37. A catalyst system as claimed in claim 36, wherein the L groups are stabilising ligands selected from chloride, bromide, iodide, hydride, alkoxide, amide, acetate, acetylacetonate, amine, ether, water, phosphine, pyridine, alkene, alkyne and N-heterocyclic carbenes.
  38. 38. A catalyst system as claimed in claim 36, wherein the L groups are reactive ligands selected from akyl, aryl, carbene and alkylidene.
  39. 39 A catalyst system as claimed in claim 36, wherein at least one L is a substrate molecule for the reaction.
  40. 40. A catalyst system as claimed in claim 36, wherein at least one L is a 3-membered carbocyclic ligand, giving a compound of formula M(L1 wherein the L groups which may be the same or different, are ligands, p is 0 to 5, and R and R' are as defined for R1 and R in claim 4.
  41. 41. A method for producing a catalyst system for catalysing olefin metathesis or cross-coupling reactions, the method comprising combining a) a source of a d-block metal, b) optionally, a further reagent, c) a source of a 3-membered carbocyclic ligand.
  42. 42. A method as claimed in claim 41, wherein the further reagent is selected from one or more of a base, an acid, a reducing agent, an oxidising agent or a ligand.
  43. 43. A method as claimed in claim 42, wherein the base is selected from one or more amines, amides, alkoxides, hydroxides, carbonates and BuLi.
  44. 44. A method as claimed in any one of claims 41 to 43, wherein the source of a d-block metal is selected from the appropriate elemental metal, the elemental metal dispersed on a suitable carrier material or a metal complex of formula MLq where M and L are as defined in claim 16 and qisan integerof 1 to6.
  45. 45. A method as claimed in any one of claims 41 to 44, wherein the source of a 3-membered carbocyclic ligand is selected from the free carbene ligand of formula R2; a carbene ligand stabilised by coordination to a Lewis acid fragment of formula wherein Z is a Lewis acid fragment; or a substituted 3,3 cyclopropene compound of formula :: wherein the X groups may be the same or different and are selected from halide, pseudohalide, weakly coordinating anion, H, a main group metal, a main group metal fragment or a d-block metal fragment MLq as defined in claim 44.
  46. 46. Use of a catalyst system as claimed in any one of claims 23 to 40 to catalyse an olefin metathesis or a cross-coupling reaction.
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EP0118801A2 (en) * 1983-03-09 1984-09-19 Sumitomo Chemical Company, Limited A catalyst for isomerization reaction
WO1993020111A2 (en) * 1992-04-03 1993-10-14 E.I. Du Pont De Nemours And Company Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
US20060173145A1 (en) * 2005-02-01 2006-08-03 Pawlow James H Multi-functionalized high-trans elastomeric polymers

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JPS58154594A (en) * 1982-03-09 1983-09-14 Zenichi Yoshida Cyclopropenylidene complex

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0118801A2 (en) * 1983-03-09 1984-09-19 Sumitomo Chemical Company, Limited A catalyst for isomerization reaction
WO1993020111A2 (en) * 1992-04-03 1993-10-14 E.I. Du Pont De Nemours And Company Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
US20060173145A1 (en) * 2005-02-01 2006-08-03 Pawlow James H Multi-functionalized high-trans elastomeric polymers

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