WO2009126831A1

WO2009126831A1 - Ruthenium olefin metathesis catalysts bearing n-heterocyclic carbene ligands with substituted backbone

Info

Publication number: WO2009126831A1
Application number: PCT/US2009/040109
Authority: WO
Inventors: Robert H. Grubbs; Cheol Keun Chung; Jean-Baptiste Bourg; Kevin Kuhn
Original assignee: Materia, Inc.; California Institute Of Technology
Priority date: 2008-04-09
Filing date: 2009-04-09
Publication date: 2009-10-15
Also published as: JP2011523625A; CN102083798A; US20110124868A1; US8877936B2; EP2276745A4; CN102083798B; EP2276745A1; JP5619724B2

Abstract

This invention relates generally to olefin metathesis, more particularly, to tri- or tetra-substituted imidazoliniυm salts which are precursors to N-heterocyclic carbene (NHC) ligands with tri- or tetra-substituted irnidazolinium rings, organometallic ruthenium complexes comprising gem di-substituted imidazoiinium NHC ligands, organometallic ruthenium complexes comprising tri- or tetra-substituted imidazoiinium NHC ligands, and to olefin metathesis methods using them. The catalysts and methods of the invention have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

Description

Ruthenium Olefin Metathesis Catalysts Bearing /V-Heterocyclic Carbene Ligands with Substituted Backbone

Government Support

[0001] This invention was supported by National Institutes of Health under Grant number GM031332. The U.S. government has certain rights in this invention.

Cross Reference to Related Applications

[0002] This application claims priority under 35 U. S. C. § 119 to U.S. provisional application serial no. 61/181,171, filed November 26, 2008; and U.S. provisional application serial no. 61/123,477, filed April 9, 2008.

Technical Field

[0003] This invention relates generally to olefin metathesis, more particularly, to tri- or tetra-substituted imidazolinium salts which are precursors to N-heterocyclic carbene (NHC) ligands with tri- or tetra-substituted imidazolinium rings, organometailic ruthenium complexes comprising gem di-substituted imidazolinium NHC ligands, organometailic ruthenium complexes comprising tri- or tetra-substituted imidazolinium NHC Mgands, and to olefin metathesis methods using them. The catalysts and methods of the invention have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

Background of the Invention

[0004] Olefin metathesis is an indispensable tool in making carbon-carbon bonds in modern organic synthesis. For recent reviews, see, e.g., (a) Grubbs, R. H. Handbook of metathesis; Wiley-VCH: Weinheim, Germany, 2003; (b) Hoveyda, A. H.; Zhugralin, A. R. Nature 2007, 450, 243-251; (c) Schrodi, Y.; Pederson, R. L. Aidrichimica Acta 2007, 40, 45- 52; (d) Grubbs, R. H. Tetrahedron 2004, 60, 7117-7140; (e) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3013-3043; (f) Nicoiaou, K. C; Bulger, P. G.; Sarlah, D. Angew. Chem., Int. Ed. 2005, 44, 4490-4527. Since the development of well-defined ruthenium-based metathesis catalysts, there has been significant effort directed towards improving the catalyst efficiency. Most notably, the substitution of a phosphine ligand of RuCI₂(PCy₃M=CHC₆H₅) for a bulky, electron-rich N- heterocyclic carbene (NHC) ligand led to metathesis catalysts with enhanced reactivity and stability. See, e.g. _ (a) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, I₁ 953-956; (b) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110; (c) Schwab, P. ; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. 1995, 34, 2039-2041. the high reactivity of NHC complexes is often attributed to the superior electron donor ability of NHC ligands in comparison to the phosphine ligands. See, .e.g., (a) Sussner, M. S. ; Plenio, H. Chem. Comm. 2005, 5417-5419. (b) Hadei, N.; Kantchev, E. A. B.; O'Brien, C. J.; Organ, M. G. Org, Lett, 2005, 7, 1991-1994.)

[0005] In addition, the use of NHC Iigand has allowed access to metathesis catalysts suitable for various applications through the modification of NHC Iigand, such as water- soluble metathesis catalysts, solid-supported catalysts, and highly active catalysts suitable for hindered substrate. See, e.g., (a) Deshmukh, P. H.; Blechert, S. Dalton Trans. 2007, 2479-2491 and references therein; (b) Stewart, I. C; Douglas, C. j,; Grubbs, R. H. Org. Lett. 2008, 10, 441-444; (c) Stewart, I. C; Ung, T.; Pletnev, A. A.; Berlin, 3. M.; Grubbs, R. H.; Schrodi, Y. Org. Lett. 2007, 9, 1589-1592.)

[0006] Although a variety of metathesis catalysts are available to address a range of problems in chemistry, it is still a challenge to obtain more robust catalysts that can be reliably applied in industrial processes. Ruthenium NHC complexes, albeit significantly more stable than the corresponding bisphosphine complexes, have limited lifetime. Recent catalyst stability studies suggested that C-H activation within the catalyst framework is responsible for the decomposition of the active ruthenium complexes. For instance, the X- ray structure of thermally degraded of ruthenium complexes bearing Λ/-mesity! or /V-phenyl- substituted NHC Iigand revealed that the Λ/-aryi substituents of NHC Iigand have been altered by the metal center (Compounds Cl-5 below). See, e.g., (a) Hong, S. H.; Wenzel, A. G.; Salguero, T. T.; Day, N. W.; Grubbs, R. H., J. Am. Chem, Soc. 2007, 129, 7961- 7968. (b) Hong, S. H.; Chlenov, A,; Day, M. W.; Grubbs, R. H., Angew, Chem., Int. Ed. 2007, 46, 5148-5151. (c) Trnka, T. M.; Morgan, 3. P.; Sanford, M. S.; Wilhelm, T. E.; Scholl, M.; Choi, T. L.; Ding, S.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 2546-2558. (d) Vehiow, K. ; Gessier, S.; Blechert, S. Angew. Chem., Int. Ed. 2007, 46, 8082-8085.

[0007] To resolve the above issue, this invention discloses further development of efficient and stable metathesis catalysts based on ruthenium NHC complexes.

Summary of the Invention

[0008] The present invention relates to imidazolinium satt NHC iigand precursor of formula (I):

X^" wherein: a) R¹ and R⁴ are methyl; and

R² and R³ are independently selected from methyl, ethyl, or ailyl, or R^z and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring;

R⁵ and R⁶ are each independently a Ci-Ci₀ alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II);

wherein, n ranges from 1 to 3; with the proviso that only one of R^s or R⁶ may be a linear alkyl group having 3 or less carbons;

R⁷ is independently selected from hydrogen, Ci-C₁₀ alkyl, CrCi₀ alkoxy, aryl, aralkyl, and one or more functional groups;

R⁸ and R⁹ are independently selected from hydrogen, C₁-C₁₀ alkyl, fluoride or chloride; with the proviso that R⁶ and R⁹ are not CrCi₀ aikyl at the same time; and, wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; or, b) R¹ is methyl;

R⁴ is H;

R² and R³ are independently selected from methyl, ethyl, allyl, or isopropyl, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring; with the proviso that R² and R³ are not both isopropyl at the same time;

R⁵ and R⁶ are each independently a C₁-C₁₀ alkyl, cycloalkyl, a fused or bridged ring, aralkyi, or a group having the structure of formula (II);

wherein, n ranges from 1 to 3; with the proviso that only one of R⁵ or R⁶ may be a linear alkyl group having 3 or less carbons; R⁷ is independently selected from hydrogen, Ci-Ci₀ aikyl, Ci-Ci₀ alkoxy, aryl, araikyl, and one or more functional groups ;

R⁸ and R⁹ are independently selected from hydrogen, Ci-Ci₀ alkyl, fluoride or chloride; and, wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; and,

X^" is an anion for the imidazolinium salt.

[0009] The invention also relates to novel N- heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of formula (III):

[0010] The catalysts of formula (III) contain the NHC ligand from the tri- or tetra- substituted imidizoladinium salt NHC ligand precursor described in formula (I) as well as the other ligands shown. The catalysts of formula (III) may also contain NHC ligands from gem di-substitued imidizoladinium salt NHC ligand precursors having the structure of formula (I) in which R¹ and R² are Ci-C₁₀ alkyl, or together form a cyclic structure, and R³ and R⁴ are hydrogen. In formula (III), X¹ and X² are independently anionic ligands; Rⁱ⁰ and R¹¹ are each independently hydrogen or a substituted or unsubstituted substituent selected from Ci-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, CrC₂₀ carboxylate, CrC₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, Ci-C_2O alkylthio, Ci-C₂₀ alkylsulfonyl and C₁-C₂₀ aikyisulfinyl; L is a neutral 2-electron donor ligand; and "m" is 1 or 2. R¹⁰ and R¹¹ may optionally be linked together to form a cyclic structure via one of the substituents mentioned above. L may optionally be linked to R¹¹ to form a chelating carbene ligand.

[0011] Another embodiment of the invention relates to an olefin metathesis reaction which contacts an olefin with an N- heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of the invention under metathesis conditions. The catalysts of the invention may be used in, for example, ring-closing metathesis (RCM), cross metathesis (CH), ring-opening metathesis polymerization (ROMP), and acyclic diene metathesis polymerization (ADMEET). Brief Description of the Drawings

[0012] Figure 1 depicts the standard activity tests of the Ruthenium catalysts in Ring Closing Metathesis (RCM) reactions to form a di-substituted olefin. [0013] Figure 2 depicts the standard activity tests of the Ruthenium catalysts in RCM reactions to form a tri-substituted olefin.

[0014] Figure 3 depicts the standard activity tests of the Ruthenium catalysts in RCM reactions to form a di-substituted olefin.

[0015] Figure 4 depicts the standard activity tests of the Ruthenium catalysts in RCM reactions to form a tri-substituted olefin.

[0016] Figure 5 depicts charts showing the standard activity tests of the Ruthenium catalysts in RCM reactions to form a di-substituted olefin and a tri-substituted olefin at 60°C.

[0017] Figure 6 depicts charts showing the standard activity tests of the Ruthenium catalysts in RCM reactions to form a tetra-substituted olefin at different temperatures. [0018] Figure 7 depicts charts comparing the catalytic activity of compound H6 and HS in RCM reactions to form a di-substituted olefin (Figure 7a), a tri-substituted olefin (Figure 7b) and a tetra-substituted olefin (Figure 7c),

[0019] Figure 8 depicts the catalytic activity of the Ruthenium catalysts in Cross- Metathesis (CM) reactions.

[0020] Figure 9 depicts the catalytic activity of the Ruthenium catalysts in Ring Opening Metathesis Polymerization (ROMP) reactions.

[0021] Figure 10 depicts the initiation kinetics studies of the compound H6. [0022] Figure 11 depicts the catalytic activity of the Ruthenium catalysts in RCM reactions using low catalysts loadings.

[0023] Figure 12 depicts the catalytic activity of the Ruthenium catalysts in RCM reactions using low catalysts loadings. [0024] Figure 13 depicts the X-Ray structural analysis of the compound H6.

Detailed Description of the Invention

1. Tri- and Tetra-substituted Imϊdazolinium Salts

[0025] In the first embodiment, the invention relates to an imidazolinium salt NHC ligand precursor of formula (I) :

x- (I).

[0026] The imidazolinium salts of the invention may be tetra- substituted or tri- substituted on the backbone of the NHC ligand - the adjacent ring carbons of the imidazole ring. The substituents are defined by R¹, R², R³ and R⁴. As shown in the Scheme 1 below, restricting the Λ/-aryl ring prevents the ruthenium complex comprising the NHC ligand from entering into the unwanted processes discussed above. The invention places bulky substituents, such as aikyl groups, on the backbone of the NHC Hgands. In addition to the stabilization effect, the backbone substitution renders the NHCs more σ-donating than the non-substituted analogues, since it was conceivable that the direct backbone substitution would have greater influence on the donor ability of NHC than the substitution on the Λ/-aryl groups.

-*- Decomposition

Scheme 1

[0027] For tetra-subsituted imidazolinium salts of the invention, R¹ and R⁴ are methyl; R² and R³ are independently selected from methyl, ethyl, or allyl, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring; R⁵ and R⁶ are each independently a C₁-C₁₀ alkyl, cycloalkyl, a fused or bridged ring, aralkyi, or a group having the structure of formula (II):

wherein n ranges from 1 to 3; with the proviso that only one of R⁵ or R⁶ may be a linear alky! group having 3 or less carbons; R⁷ is independently selected from hydrogen, Ci-C₁₀ alkyl, Ci-Ci₀ alkoxy, aryl, aralkyl, and one or more functional groups; R⁸ and R⁹ are independently selected from hydrogen, C₁-Ci₀ alkyl, fluoride or chloride: with the proviso that R^s and R⁹ are not CrCi₀ alkyi at the same time; and wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; and X^" is an anion for the imidazoiinium salt.

[0028] For tri-substituted imidazoiinium salts of the invention, R¹ is methyl; R⁴ is H; R² and R³ are independently selected from methyi, ethyl, ally!, or isopropyl, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8~membered tarbocySic ring: with the proviso that R² and R³ are not both isopropyl at the same time; R^s and R⁶ are each independently a Ci-Ci₀ alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II) :

wherein n ranges from 1 to 3; with the proviso that only one of R⁵ or R⁶ may be a linear alky! group having 3 or less carbons; R⁷ is independently selected from hydrogen, C₁-C₁₀ alkyS, C₁-C₁₀ alkoxy, aryl, aralkyl, and one or more functional groups; R⁸ and R⁹ are independently selected from hydrogen, C₁-C₁₀ alkyi, fluoride or chloride; wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; and X^" is an anion for the imidazoiinium salt. [0029] In preferred embodiments of these tri-substituted or tetra- substituted imidazoiinium salts, R² and R³ are methyl, or R² and R³ together with the carbons carrying them form a fused 6- membered carbocylic ring; and R⁵ and R⁶ are independently selected from the group consisting of isopropyi, tertbυtyl, neopentyl, phenyl, or a group having the structure of formula (II):

wherein n ranges from 1 to 3; R⁷ is independently selected from hydrogen, C₁-C₁₀ alkyl, C₁- Cio alkoxy, aryi, aralkyl, and one or more functional groups; and R⁸ and R⁹ are independently selected from hydrogen, C₁-Ci₀ alkyl, fluoride or chloride: with the proviso that R⁸ and R⁹ of the tetra-substituted imidazolinium salts are not Ci-Ci₀ alkyl at the same time. In even more preferred embodiments, R² and R³ are methyl; R⁵ and R⁶ are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyl, o-difluorophenyl, o-dichlorophenyl or o-isopropySphenyl. For tetra-substituted imidazolinium salts, X^" is preferably chloride, bromide, iodide, tetrafluroborate (BF₄) or trifluoroacetate (CF₃COO); for tri-substituted imidazolinium salts X^" is preferably chloride, tetrafluroborate(BF₄) or trifluoroacetate (CF₃COO).

2. Preparation of Imidazolinium Salts

[0030] The tetra- or tri~ substituted imidazolinium salts NHC ligand precursors of formulas (I) used to form the Ruthenium catalysts of the invention may be prepared from diamine derivatives bearing desired substituents and substitution pattern, as shown in the examples below. Typically, the diamine is dissolved in diethyl ether and treated with a solution of hydrogen chloride to precipitate the diamine hydrochloride salt. The diamine hydrochloride salt is reacted with large excess of triethyl orthoformate to give the desired imidazolinium chloride salts NHC ligand precursor of formula (I). Alternatively, the diamine compound can also form salt with trifluoroacetic acid or tetrafluoroborate acid, which is also reacted with large excess of triethyl orthoformate to give the desired imidazolidinium salts NHC Hgand precursor of formula (I). 3. N-Heterocγclic Carbene (NHC) Ruthenium Catalysts of the Invention [0031] The invention also relates to N- heterocyclic carbene (NHC) ruthenium olefin metathesis catalysts. Advantageously, the catalysts of the invention display greater efficiency/activity than current olefin metathesis catalysts for catalyzing ring-closing metathesis (RCM) reactions to form tetra-substituted cyclic olefins. The catalysts also perform the other known metathesis reactions in the family of metathesis reactions discussed above. The catalysts are also particularly useful in cross-metathesis to prepare tri-substituted olefins, and di-substituted olefins that are further substituted at the allylic carbon. The /V-heterocyclic carbene (NHC) ruthenium olefin metathesis catalysts of the invention have the following general formula (III):

-m

[0032] The NHC Iigand in the ruthenium catalyst of formula (III) is derived from the imidazolinium salt NHC Iigand precursor of formula (I) described above, with formula (IV):

[0033] For ruthenium catalyst derived from the tetra-subsituted NHC Iigand of the invention, R¹ and R⁴ are methyl; R² and R³ are independently selected from methyl, ethyl, or allyl, or R² and R³ together with the carbons carrying them form a fused 6~, 7- or 8- membered carbocylic ring; R⁵ and R⁶ are each independently a C₁-C₁₀ alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II):

wherein n ranges from 1 to 3; with the proviso that onty one of R⁵ or R⁶ may be a linear alkyl group having 3 or less carbons; R⁷ is independently selected from hydrogen, Ci-Ci₀ alkyl, C₁-Ci₀ alkoxy, aryl, aralkyi, and one or more functional groups; R⁸ and R⁹ are independently selected from hydrogen, CrCi₀ alkyl, fluoride or chloride: with the proviso that R⁸ and R⁹ are not C₁-C₁₀ alkyl at the same time; and wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹.

[0034] For ruthenium catalyst derived from the tri-subsituted NHC ligand of the invention, R¹ is methyl; R⁴ is H; R² and R³ are independently selected from methyl, ethyl, ally!, or isopropyl, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring: with the proviso that R² and R³ are not both isopropyl at the same time; R⁵ and R⁶ are each independently a Ci-Ci₀ alkyi, cycloalky!, a fused or bridged ring, aralky!, or a group having the structure of formula (II):

wherein n ranges from 1 to 3: with the proviso that only one of R^s or R⁶ may be a linear alkyi group having 3 or less carbons; R⁷ is independently selected from hydrogen, CrCi₀ alkyl, C₁-Ci₀ alkoxy, aryl, aralkyl, and one or more functional groups; R⁸ and R⁹ are independentiy selected from hydrogen, Ci-Ci₀ alkyl, fluoride or chloride. R² and/or R³ may form a cyclic structure with one or both of R^s and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹.

[0035] In preferred embodiments of the ruthenium catalyst derived from the tri- substituted or tetra- substituted NHC ligand of the invention, R² and R³ are methyl, or R² and R³ together with the carbons carrying them form a fused 6- membered carbocylic ring; and R⁵ and R⁶ are independently selected from the group consisting of isopropyl, tertbutyl, neopentyl, phenyl, or a group having the structure of formula (II):

wherein n ranges from 1 to 3; R⁷ is methyl, fluoride or chloride; and R⁸ and R⁹ are independently selected from hydrogen, C₁-C₁₀ alkyi, fluoride or chloride: with the proviso that R^a and R⁹ of the tetra-substituted imidazolinium salts are not Ci-Ci₀ alkyl at the same time. In even more preferred embodiments, R² and R³ are methyl; and R⁵ and R⁵ are independently selected from phenyl, mesityl, o-tolyl, m-toiyl, p-tolyl, o-difluorophenyl, o-dichlorophenyl or o-isopropylphenyi.

[0036] One embodiment of the NHC ligand in the ruthenium catalyst of formula (III) of the invention includes the ruthenium catalyst derived from the gem di -substituted N- heterocyclic carbene (NHC) ligand of formula (IV):

wherein R¹ and R² are C₁-Ci₀ alkyl, or together form a cyclic structure; R³ and R⁴ are H; R⁵ and R⁶ are each independently a C₁-C₁₀ alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II):

wherein, n ranges from 1 to 3: with the proviso that only one of R⁵ or R⁶ may be a linear alkyi group having 3 or less carbons; R⁷ is independently selected from hydrogen, C₁-C₁₀ aikyl, C₁-C₁₀ alkoxy, aryi, araiky!, and one or more functional groups; R⁸ and R⁹ are hydrogen, Ci-Ci₀ alkyl, fluoride or chloride. R¹ and/or R² may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹. [0037] In the catalysts of formula (III), X¹ and X² are independently anionic ligands. Preferably, X¹ and X² are halide, or one of the following groups; Ci-C_2O alkyl, aryl, C₁-C₂O alkoxide, aryloxtde, C₃-C₂₀ alkyldiketonate, aryldiketonate, C₁-C_2O carboxylate, arylsulfonate, C₁-C₂₀ alkylsulfonate, Ci-C₂₀ alkylthio, C_I-C₂₀ alkylsulfonyl, or Ci-C₂₀ alkylsulfinyl. Optionally, X¹ and X² may be substituted with one or more moieties selected from the group consisting of C₁-C₁₀ alky!, Ci-C₁₀ alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from halogen, Ci-C₅ alkyl, Ci-C₅ alkoxy, and phenyl, In more preferred embodiments, X¹ and X² are halide, benzoate, C₁-C₅ carboxylate, C₁-C₅ aikyl, phenoxy, Ci-C₅ alkoxy, C₁-C₅ alkylthio, aryl, and C_x-C₅ alkyl sulfonate. As discussed below, the other ligands in a catalyst of the invention, when substituted, may also contain such substituents. In even more preferred embodiments, X¹ and X² are each halide, CF₃ CO₂, CH₃,CO₂, CFH₂ CO₂, (CH₃)₃ CO, (CF₃)₂ (CH₃)CO, (CF₃)(CH₃)₂CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate, In the most preferred embodiments, X¹ and X² are each chloride.

[0038] R¹⁰ and R¹¹ are each independently hydrogen or a substituted or unsubstituted group selected from the group consisting of Ci-C₂₀ aikyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, Ci-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, C_t-C₂₀ alkylthio, Ci-C₂₀ 20 alkylsulfonyl and C₁-C₂₀ alkylsulfinyl. Optionally, each of the R¹⁰ or R¹¹ substituent group may be substituted with one or more moieties selected from the group consisting of Ci-C₁₀ alkyl, C₁-Ci₀ alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a Ci-C₅ alkyl, C₁-C₁₅ alkoxy, and phenyl. Moreover, R¹⁰ and R¹¹, as well as any other of the catalyst ligands, may further include one or more functional groups as long as they do not defeat the activity of the catalyst. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. R¹⁰ and R¹¹ may optionally be linked together to form a cyclic structure via one of the substituents mentioned above.

[0039] In preferred embodiments of these catalysts, the R¹⁰ substituent is hydrogen, C₁- C₅ alkyi or aryl and the R¹¹ substituent is selected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂Q alkenyl, and aryl. In even more preferred embodiments, the R¹¹ substituent is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of Ci-C₅ alkyl, C₁-C₅ alkoxy, phenyl, and a functional group, In especially preferred embodiments, R¹¹ is phenyl or vinyl substituted with one or more moieties selected from the group consisting of chloride, bromide, iodide, fluoride, -NO₂, -NMe₂, methyi, methoxy and phenyl. In the most preferred embodiments, the R¹¹ substituent is phenyl or -C=C(CH₃J₂. [0040] L may be any neutral 2-electron donor ligand known in the art. The variable "m" defines the number of neutral donor ligands, L. The variable "m" is 1 or 2 and preferably 1. When ^wm" is 1, L is any neutral 2-eSectron donor Mgand, L may be linked to R¹¹ forming a chelating arbine ligand. When "m" is 2, L is a heteroarene iigand such as pyridine or substituted pyridine. See U.S. Patent Nos. 6,759,537 and 6,818,586, herein incorporated by reference in their entirety; for examples of suitable heteroarene ligands. Preferably, the heteroarene ligand is pyridine or substituted pyridine.

[0041] In a preferred embodiment, L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thtoether, In more preferred embodiments, L is a phosphine of the formula PR'R"R'", where R', R", and R'" are each independently aryl; CrCi₀ alkyl (in particular, a primary or secondary alkyl); or C₃-C₆ cycloalkyl. In the most preferred embodiments, L is selected from the group consisting of P(cyclohexyl}₃, P(cyclopentyl)₃, P(isopropyl)₃, and P(phenyl)₃.

[0042] In a preferred embodiment, L may be linked to R¹¹ forming a chelating arbine ligand. The L portion of the chelating arbine ligand is still a 2-electron donor ligand when linked to R¹¹. L may or may not be linked to R¹¹ through a spacer moiety. U.S. Patent 6,921,735 describes chelating arbine ligands and is incorporated herein by reference for examples of how the ligand and R substituent on the arbine can be linked through various spacer moieties. The spacer moiety may be substituted or unsubstituted. [0043] Preferred catalysts of the invention where L and R¹¹ are (inked include those represented by formula (V):

[0044] In formula (V), NHC is an N-heterocyclic carbene (NHC) ligand of formula (IV). Y is a heteroatom selected from oxygen, sulfur, nitrogen, or phosphorus. X¹ and X² are independently anionic ligands. Z is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, functionalized alkyl, or functionalized aryl, wherein the functional group(s) may independently be selected from alkoxy, aryloxy, halogen, carbonyl, carboxyiic acid, ketone, aldehyde, nitrate, nitrile, nitro, cyano, isocyanate, hydroxy!, ester, ether, amine, imine, amide, sulfide, sulfonyl, sulfinyl, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or combinations thereof; each optionally substituted with an alkyl, halogen, alkoxy, aryl, aryloxy, or heteroaryl moiety, R^a, R^b, R^c, and R^d are independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, functionalized alkyl, or functionalized aryl, wherein the functional group(s) may independently be selected from alkoxy, aryloxy, halogen, carbonyl, carboxyiic acid, ketone, aldehyde, nitrate, nitrile, nitro, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, sulfonyl, sulfinyl, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or combinations thereof; each optionally substituted with an alkyl, halogen, alkoxy, aryl, aryloxy, or heteroaryl moiety, wherein any two or more of R^a, R^b, R^c, and R^d may be independently linked through hydrocarbon or functionalized hydrocarbon groups forming an aliphatic or aromatic ring.

[0045] Preferred catalysts of the invention where L and R¹¹ are linked may also include the following :

\ 5

[0046] Examples of ruthenium complexes with chelating arbine ligands, ligands linking the L iigand and the Rⁿ substitutent, are also described in Kingsbury, J, S.; Harrity, J. P. A.; Bonitatebus, P. ]., Jr.; Hoveyda, A. H. J. Am, Chem. Soc. 1999, 121, 791 and Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168. Preferably, R¹¹ is linked to L via spacer group being 2-5 atoms in iength between L and R¹¹, for example via an aikyl group, a cycoloalkyl group, or an aryl group. A preferred spacer group is a substituted or unsubstituted phenyl group. 4. Synthesis of Catalysts

[0047] The ruthenium catalysts of the invention may be prepared using methods known in the art. In general, the catalysts of the present invention are prepared via a ligand exchange reaction, for example, by substituting an NHC ligand for one of the neutral electron donor ligands in a first generation ruthenium carbene complexes (discussed above). For example, a Ruthenium Phosphine complex of the invention can be prepared by replacing a phosphine ligand in a complex of the general formula (PCy_S)₂(X)₂Ru=CHC₆H₅ with an NHC ligand described above. Example 2 illustrates preparation of ruthenium catalysts of the invention by this method. Ruthenium Ether complex of the invention can be prepared by replacing a phosphine ligand in a complex of the genera! formula (PCy₃)(X)₂Ru=CH-O-JPrC₆H₅ with an NHC ligand described above. Examples 3, 6 illustrate preparation of ruthenium catalysts of the invention by this method. As discussed in the Background of the Invention, these synthetic procedures are known in the art,

5. Metathesis Reactions

[0048] The ruthenium catalysts of the invention are particularly efficient olefin metathesis catalysts. Accordingly, one embodiment of the invention is an olefin metathesis reaction which contacts an olefin with an /V-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of the invention under metathesis conditions. The catalysts of the invention may be used in, for example, ring-closing metathesis (RCM), cross metathesis (CM), self metathesis (which is a type of cross metathesis), ring-opening metathesis polymerization (ROMP), and acyclic diene metathesis polymerization (ADMET). [0049] The metathesis conditions for the catalysts of the invention are the same as those used in other olefin metathesis reactions and with other known olefin metathesis catalysts. Generally speaking, the olefin metathesis reactions are run at a temperature ranging from about 10 ⁰C to about 70 °C and for a time period ranging from about 5 minutes to about 24 hours. The catalysts of the invention may be used in the same amounts as know for other olefin metathesis catalysts. Typically, about 1 to about 10 mol% of the catalyst is used and more often about 1 to 5 mo!%.

[0050] The ruthenium catalysts of the invention are particularly useful in metathesis reactions for the production of tetra-substituted cyclic olefins. The catalysts of the invention have significantly increased efficiency/activity for the preparation of tetra-substituted cyclic olefins via olefin metathesis. Examples:

[0051] General experimental conditions for Examples 1-8: All reactions involving metal complexes were conducted in oven-dried glassware under a nitrogen atmosphere with anhydrous solvents, using standard Schlenk and glovebox techniques. Anhydrous solvents were obtained via elution through a solvent column drying system. (See Pangborn, A, B,; Giardeϋo, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518-1520.) RuCl₂(PCy₃)₂(=CHC₆H₅) was obtained from Materia, Inc. Silica gel used for the purification of organometailic complexes was obtained from TSI Scientific, Cambridge, MA (60 A, pH 6.5-7.0). NMR chemical shifts are reported in ppm downfield from Me₄Si, by using the residual solvent peak as internal standard for ¹H and ¹³C, and H₃PO₄ (δ 0.0) for ³¹P. Data for NMR spectra are reported as follows: chemical shift (δ ppm), multiplicity, coupling constant (Hz) and integration. IR spectra were recorded on a Perkin-Elmer Paragon 1000 Spectrophotometer. Gas chromatography data was obtained using an Agilent 6850 RD gas chromatograph equipped with a DB-Wax Polyethylene Glycol capillary column (J&W Scientific). X-ray crystallographic structures were obtained by the Beckman Institute X-ray Crystallography Laboratory of the California Institute of Technology. Unless otherwise stated, the screening of the catalysts, in ring-closing metathesis (RCM), cross metathesis (CM), and ring-opening metathesis polymerization reactions (ROMP), was conducted according to literature procedures, (see Ritter, T.; Hejl, A.; Wenzel, A. G.; Funk, T. W.; Grubbs, R. H. Organometailics 2006, 25, 5740-5745.) The initiation kinetics studies were conducted according to literature procedures, (see Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6543-6554.)

[0052] Example 1. Preparation of NHC ligand precursors (S): [0053] Procedure A: A diethyl ether solution of the desired diamine was treated with a solution of hydrogen chloride (2 eq) to precipitate the diamine hydrochloride salt. The white solid was collected by filtration and washed with copious amount of diethyl ether. The solid was placed in a flask and triethyl orthoformate (large excess) was added. The resulting mixture was stirred at 130 °C for 5 to 10 min then cooled. After cooling to room temperature, the white solid was collected by filtration washing with large amount of diethyl ether and then with acetone to give the desired imidazolidinium chloride salt S. [0054] Procedure B: (See Jazzar, R.; Bourg, J. -B.; Dewhurst, R. D.; Donnadieu, B.; Bertrand, G. J. Org. Chem. 2007, 72, 3492-3499) To a THF solution (40 mL) of the corresponding formamidine, (1 eq) at -78 ⁰C was added a solution of π-BuLi in hexanes (1 eq). The mixture was stirred for 30 minutes, then was allowed to warm to r.t. and stirred for a further 12 hours. The mixture was again cooled to -78 ⁰C, and 3-bromopropene {1 eq) or 3-bromo-2-methyipropene (1 eq) was slowly added. The mixture was stirred for 30 minutes at -78 ⁰C then heated at 50 ⁰C for 12 hours. Removal of the volatiles under vacuum and extraction with hexanes afforded the corresponding alkylated derivative. [0055] An oven dried, argon flushed, sealable Schlenk tube with a Teflon stopcock was loaded with the alkylated derivative (1 eq), toluene and was cooled to O⁰C, at which point was added a solution of HCI in Et₂O (2.0 M, 1 eq). Precipitation of a white powder was immediately observed. After 15 minutes at O⁰C the mixture was left to warm to r.t. and stirred for an additional 15 minutes. The mixture was heated at 110⁰C for 24 hours, after which time the volatiles were removed under vacuum and the resulting salt washed with toluene and ether to afford the desired imidazolinium salts. [0056] Example Ia, l,3-DimesityI-4-Methyl-imidazolinium chloride (Si)

Prepared according to procedure B. ¹H NMR (500 MHz, CDCl₃): δ 9.70 (s, IH), 6.88 (m, 4H), 5.02 (m, IH), 4.75 (pseudo-t, J = 11.5 Hz, IH), 3.85 (dd, J = 8.5 Hz, J = 12.0

Hz, IH), 2,40-2.10 (m, 18H), 1.50 (d, J = 6.5 Hz, 3H). ¹³C NMR (75 MHz, CDCI₃): δ 159.8, 140.4, 140.2, 135.8, 135.3,

135.1, 134.8, 130.4, 130.3, 130.2, 130.1, 130.0 (br s), 128.8, 60.5, 58.3, 21.1, 21.0, 19.0, 18.8, 18.5, 18.0 (br s). HRMS Calc'd for C₂₂H₂₉N₂: 321.2331. Meas: 321.2321. [0057] Example Ib. l,3-dimesityl-4,4-Dϊmethyl-imidazoIinium chloride (S2)

Compound S2 is described in the literature. (See Jazzar, R.; Bourg, J. -B.; Dewhurst, R. D.; Donnadieu, B,; Bertrand, G. 3.

Org. Chem. 2007, 72, 3492-3499)

Su-.

[0058] Example Ic. (C/s-4,5)-l,3-dimesity[-4,5-DimethγI-imidazol!nium chloride (S3)

Prepared according to procedure A. ¹H NMR (300 MHz, CDCI₃): δ 9.77 (s, IH), 6.98 (s, 2H), 6.96 (s, 2H), 5.13 (m, 2H), 2.43 (s, 12H), 2.39 (s, 12H), 2.29 (s, 6H), 1.33 (d, J =

6.0 Hz, 6H). ¹³C NMR (75 MHz, CDCl₃): δ 159.0, 140.3, 135.8, 135.4, 130.4, 130.3, 129.0, 62.4, 21.1, 19.1, 18.7, 12.4.

HRMS Calc'd for C₂₃H_3xN₂: 335.2487. Meas: 335.2495.

[0059] Example Id. l,3-dimesityl-4,4,5-trimethyl-imidazolinϊum tetraflυoroborate (S4) A mixture of diamine (1.62 g, 4.78 mmol), ammonium tetraffuoroborate (0.75 g, 7.17 mmoi), and tπethyl orthoformate (12 ml) was stirred at 120 ⁰C for 10 mm and

cooled to room temperature. The precipitation was collected

S4 by filtration, and the solid was redissolved in CH₂CI₂. After the tnsolubie material was filtered off, the filtrate was evaporated under vacuum, and the residue was recrystallized in ethyl acetate to give S4 as a white solid (543 mg, 1.24 mmol, Y = 26%). ¹H NMR (300 MHz, DMSO-d6): δ 9.00 (s, IH), 7.13 (s, 2H), 7.11 (s, 2H), 4.71 (q, J = 6.9 Hz, IH), 2.34-2.29 (m, 18H), 1.52 (s, 3H), 1.36 (s, 3H), 1.19 (d, J = 6.9 Hz, 3H). ¹³C NMR (75 MHz, DMSO-d6): δ 159.0, 139.7, 137.5, 136.9, 136.0, 135.8, 130.2, 130.1, 129.8, 129.2, 128.3, 73.5, 67.7, 26.3, 20.5, 20.5, 19.3, 19.1, 18.2, 17.9, 11.9. ¹⁹F NMR (282 MHz, DMSO-dό): δ -148.7. HRMS Calc'd for C₂₄H₃₃N₂: 349.2644. Meas: 349.2648.

[0060] Example Ie. ljS-bisCl_jβ-difluorophenyl^^S_jS-tetramethyl-imidazolin- 2-ium chloride (S5)

A mixture of diamine (370 mg, 0.895 mmol) and tπethyl orthoformate (3 ml) was heated at 130 °C for 1.5 hr, then cooled to room temperature. White sohd which was formed on adding diethyl ether, was collected by filtration (80 mg, 0.207 mmoi, Y =

S₅ 23%). ¹H NMR (300 MHz, DMSO-dδ): δ 9.56 (s, IH), 7.81-7.74

(m, 2H), 7.54-7.49 (m, 4H), 1.44 (s, 12H). ¹⁹F NMR (282 MHz, DMSO-c/6): δ -117.3. HRMS Calc'd for C₁₉H₁₉F₄N₂ ⁺: 351.1484. Meas: 351.1472. [0061] Example If: l,3-diphenyl-4,4_/5,5-tetramethy[-imidazol-2-ium chloride (S6) .00 g, 58.0 mmol), aniline (10.80 5 ml) was stirred at room ow crystalline solid was collected mall amount of ethanol to yield

of the desired dπmme. A solution of the dnmine (3.14 g, 13.29 mmol) tn dry benzene was placed in a flask equipped with a reflux condenser, and added a solution of methylmagnesium chloπde in tetrahydrofuran (3 0 M, 17.7 ml, 53.2 mmol). The resulting solution was stirred at refluxing temperature for overnight. After cooled to room temperature, the reaction mixture was slowly added saturated aqueous solution of ammonium chloπde. The organic layer was separated and the aqueous layer was extracted with ethyl acetate three times. The combined organic layer was washed with brine, dried over magnesium sulfate, and purified by flash chromatography on silica (eluent: hexanes/ethyl acetate = 30/1) to yield the desired diamine as a yellow oil (1.32 g, 4.90 mmol, Y = 37%). The diamine was dissolved in diethyl ether (10 ml) and treated with a solution of hydrogen chloride (4 M in dioxane) to precipitate the diamine hydrochloride salt. The solid collected by filtration was added triethyl orthoformate (1.5 ml) and stirred at 120 ⁰C for 17 hours. After cooled to room temperature, the tan colored solid was collected by filtration and washed with diethyl ether and acetone to give the desired imidazolidinium chloride salt S6 as a white powder (1.12 g, 3.56 mmol, Y = 73%). ¹H NMR (300 MHz, CD₂CI₂) : δ 9.37 (s, IH), 7.69-7.66 (m, 4H), 7.54-7.52 (m, 6H)₇ 1.46 (s, 12H). ¹³C NMR (75 MHz, CD₂Ci₂) : δ 156.8, 133.3, 130.4, 130.0, 128.6, 74.0, 21.5. HRMS Calc'd for C₁₉H₂₃N₂: 279.1861. Meas: 279.1852.

[0062] Example Ig: l,3-di-o-tolyl-phenyI-4,4,5,5-tetramethyl-imidazoi-2-ium chloride (S7)

A mixture of 2,3-butandione (2.00 g, 23.23 mmol), σ-toluidine (5.00 g, 46.66 mmol), and ethanol (ca. 2 ml) was stirred at room temperature for 1 day. The yellow crystalline solid was collected by filtration and rinsed with a small amount of

ethanol to yield 3.42 g (12.97 mmol, Y = 56%) of the desired dϊimine. A solution of the diimtne (3.00 g, 11.35 mmol) in dry benzene was placed in a flask equipped with a reflux condenser, and added a solution of methyimagnesium chloride in tetrahydrofuran (3.0 M, 11.3 ml, 45.4 mmol). The resulting solution was stirred at refluxing temperature for overnight. After cooled to room temperature, the reaction mixture was slowly added saturated aqueous solution of ammonium chloride. The organic layer was separated and the aqueous layer was extracted with ethyl acetate three times. The combined organic layer was washed with brine, dried over magnesium sulfate, and purified by flash chromatography on silica (eluent: hexanes/ethyl acetate = 30/1) to yield the desired diamine as a yellow oil (2.25 g, 7.60 mmol, Y = 67%). The diamine was dissolved in diethyl ether (10 ml) and treated with a solution of hydrogen chloride (4 M in dioxane) to precipitate the diamine hydrochloride salt. The solid was collected by filtration and rinsed with ample amount of diethyl ether then with acetone to give the desired amine salt as a white powder (2.19 g, 5.93 mmol, Y = 78%). A mixture of the diamine salt (330 mg, 0.89 mmol) and triethyl orthoformate (1.5 ml) was placed in a vial and stirred at 120 °C for 18 hours. After cooled to room temperature, the tan colored solid was collected by filtration and washed with diethyl ether. (S7, 64 mg, 0.187 mmol, Y = 21%). ¹H NMR (300 MHz, CDCI₃) : δ 9.38 (br s, IH), 7.58 (deformed d, 2H), 7.40-7.30 (m, 6H), 2.47 (s, 6H), 1.50 (s, 12H). ¹³C NMR (75 MHz, CDCl₃): δ 157.9, 136.3, 131.8, 131.3, 130.4, 130.4, 127.2, 74.0, 21.6, 18.8. HRMS Calc'd for C₂₁H₂₇N₂: 307.2174. Meas: 307.2162. [0063] Example Ih: l-Mesϊtγl-4,4-dimethyI-3-phenyl-4,5-dihydro-lH-imida2θl- 2-ium chloride (SS)

2-bromo-2-methylpropanoyl bromide (4.50 g, 19.57 mmol) was added to a mixture of 2,4,6-trimethylaniline (2.41g, 17.78 mmol), triethySamine (3.60 g, 35.56 mmol), and CH₂CI₂ (20 ml) at 0 ⁰C under Ar atmosphere. The cooling

bath was removed after the addition was completed, and the reaction mixture was stirred at room temperature for 1.5 hour, after which time the mixture was diluted with CH₂CI₂ (20 ml) and added aqueous solution of NH₄CI. After the aqueous phase was separated, the organic layer was washed with brine and dried over anhydrous MgSO₄. Filtration and concentration of the filtrate gave 2-bromo-/V-mesityl-2- methylpropanamide as a pale yellow solid (5.05g, 17.78 mmol, 100%). A solution of this amide (284 mg, 1.00 mmol) in dry THF (5 ml) was added to a mixture of sodium hydride (60% in mineral oil, 80 mg, 2.00 mmol), aniline (112 mg, 1.20 mmol) and THF (5 ml), and the resulting mixture was stirred for overnight at room temperature. The mixture was then added an aqueous solution of NH₄C! (15 ml), extracted with ethyl acetate (20 ml x 2), and the combined organic layer was washed with brine then dried over anhydrous Na₂SO₄. After filtration, the filtrate was concentrated under vacuum, and the residue was purified by column chromatography on silica (eluent: Hexane/Ethyl acetate = 5/1 ~ 4/1) to give the amide as a white solid (255 mg, 0.86 mmol, Y = 86%). ¹H NMR (300 MHz, CDCI₃): δ 8.35 (s, IH), 7.25-7.17 (m, 2H), 6.84-6.71 (m, 5H), 3.98 (s, IH), 2.23 (s, 3H), 2.11 (s, 6H), 1.63 (s, 6H). ¹³C NMR (75 MHz, CDCI₃): δ 173,8, 144.5, 136.4, 134.8, 131.0, 129.0, 119.2, 116.2, 58.4, 26.2, 20.8, 18.6. IR: 3341 (m), 3310 (s), 2987 (w), 1666 (s), 1607 (m), 1488 (s), 1376 (m), 1318 (m), 1264 (m), 1210 (m), 1162 (m), 850 (m), 749 (s), 696 (m) cm^"1. HRMS Calc'd for Ci₉H₂₄N₂O: 297.1967, Meas: 297.1956.

[0064] A solution of the amide (100 mg, 0.337 mmol) in dry dimethoxyethane (2 ml) was added lithium aluminum hydride (80 mg, 2.1 mmol), and the mixture was refluxed for 1 day. After cooling to room temperature, the reaction was quenched by adding H₂O (0.08 ml), 15% aqueous NaOH (0,08 ml), and H₂O (0.24 ml) successively. The white precipitation was filtered off and the filtrate was purified by column chromatography on silica (eluent: Hexane/Ethyl acetate = 10/1) to give Λ/¹-mesityl-2-methyl-Λ/²-phenylpropane-l,2-diamine as a pale yellow solid (54 mg, 0.192 mmol, Y = 57%). The diamine (1.45 g, 5.14 mmol) was converted to the corresponding dihydrochloride salt (1,83 g, 5.14 mmol, 100%) by treating with HCi solution (4 M in dioxane). A mixture of this salt (500 mg, 1.4 mmol) and triethy! orthoformate (4.7 ml) was stirred at 130 ⁰C for 5 min then cooled. After cooling to room temperature, the white precipitation was collected by filtration washing with large amount of diethyl ether and then with acetone to give the desired imidazolidϊnium chloride salt (367 mg, 1.12 rnmoi, Y = 80%). ¹H NMR (300 MHz, CDCI₃): δ 9.76 (s, IH), 7.65-

7.62 (m, 2H), 7.49-7.47 (m, 3H), 6.92 (s, 2H), 4.13 (s, 2H), 2.39 (s, 6H), 2.27 (s, 3H), 1.69 (s, 6H). ¹³C NMR (75 MHz, COCI₃) : δ 158.4, 140.2, 134.9, 132.3, 130.2, 130.0, 129.9, 129.8, 127.4, 68.6, 63.7, 26.7, 20.9, 18.1. IR: 3401 (m), 2975 (w), 1624 (s), 1592 (m), 1301 (w), 1263 (m), 1219 (m), 856 (w), 776 (w) cm^"1. HRMS Calc'd for C₂₀H₂₅N₂: 293.2018. Meas: 293.2021.

[0065] Example 2, Synthesis of Ruthenium Catalysts (Phosphine complexes, P): [0066] General procedure: To a solution of imidazotinium salt S (I eq) in dry benzene (or toluene) was added KHMDS (1.1 eq) under nitrogen atmosphere, and the resulting mixture was stirred at room temperature for a few minutes, after which time, RuCI₂(PCy₃M=CHC₆H₅) (1 eq) was added in one portion. The reaction mixture was stirred at the designated temperature and time, and then concentrated under vacuum. Dry hexane was added to the dark brown residue, and the mixture was stirred at room temperature for 20 minutes. The brown precipitation was collected by filtration and washed with hexane and then with methanol to give the desired ruthenium complexes P. Alternatively, catalysts P can be purified by column chromatography. [0067] Example 2a. RuCI₂(4_/4-dimethyl-l,3-dimesϊtyl-imidazolin-2- yiidene)(=CH~Ph)(PCy₃) (P2)

Stirred at 70 ⁰C for 1 hour. ¹H NMR (500 MHz, C₆D₆, 25°C): δ¹⁹-⁷² (^s' °-^45H)' ¹⁹-⁶⁹ (^s' 0.55H), 7.32-6.96 (m, 9H), 3.33-3.12 (m, 2H), 3.09-0.95 (m, 57H). HRMS

Calc'd for C₄₈H₆₉CI₂N₂PRu : 876.3619. Meas: 876.3588.

P2

[0068] Example 2b. RuCl₂(4,4,5-trimethyI-l,3-dimesityl-imidazolin-2- ylidene)( = CH-Ph)(PCy₃) (P4)

Stirred at 70 ⁰C for 1 hour. ¹H NMR (500 MHz, C₆D₆, 25⁰C): δ 19.69 (br s, IH), 7.32-6.90 (m, 9H), 4.12-3.91 (m, IH),

P4 3.11-0.55 (m, 60H). HRMS Calc'd for C₄₉H₇₁Cl₂N₂PRu: 890.3776. Meas: 890.3765. [0069] Example 2c. RuCl_a(4,4,5,5-Tetramethyl-l,3-dϊphenyiιmidazoIin-2- ylϊdene)(=CH-Ph)(PCy₃) (P6)

Stirred overnight at RT. ¹H NMR (500 MHz, C₆D₆): δ 19.61 (d, J = 3.8 Hz, IH), 8.11 (d, J = 6,7 Hz, 2H), 7.36-6.67 (m, 1^3H)' 2.25-2.18 (m, 3H), 1.68-1.54 (m, 15H), 1.34-1.25 (m, 6H), 1.17-1.06 (m, 9H), 0.87 (s, 6H), 0.85 (s, 6H). ¹³C

NMR (125 MHz, C₆D₆): δ 300.8, 217.2, 216.6, 151.8, 139.3, 137.9, 133.9, 131.1, 129.5, 129.4, 129.2, 129.1, 128.9,

128.7, 128.5, 128.3, 128.0, 127.8, 127.7, 70.8, 70.7, 70.5,

33.4, 33.3, 29.6, 28.5, 28.4, 27.1, 22.5, 22.0. ³¹P NMR (121 MHz, C₆D₆): δ 22.35. [0070] Example 2d. RuCI₂(l-Mesityl-4,4-dϊmethyl-3-phenylϊmidazoiϊn-2- ylidene)(=CH-Ph)(PCy₃) (PS)

151.8, 138.3, 137.7, 136.9, 136.1, 135.0, 129.7, 129.4, 129.1, 128.9, 128.6, 128.2, 65.9, 65.2, 32.7, 32.5, 29.2, 28.3, 28.2, 27.7, 26.7, 21.2, 18.8. IR (CD₂CI₂): 2931 (s), 2852 (m), 1987 (w), 1487 (m), 1447 (m), 1400 (m), 1301 (m), 1175 (m), 778 (w) cm^*1. HRMS Calc'd for C₄₅H₆₃CI₂N₂PRu : 834.3150. Meas: 834.3165.

[0071] Example 3, Synthesis of Ruthenium Catalysts (Ether complexes, H);

General procedures:

[0072] Procedure C: To a solution of imidazolinium salt (1 eq) in toluene was added

KHMDS (1.1 eq), and the resulting solution was stirred at room temperature for a few minutes. RuCl₂(PCy₃)(=CH~o-iPrPh) (1 eq) was then added, and the mixture was stirred for the designated time and temperature (vide infra). After cooling to room temperature, the mixture was purified by column chromatography on TSI silica (eluent: n-pentane/diethyl ether - 2/1) to give the titled compounds H as a green solid

[0073] Procedure D: A mixture of phosphine complexe (1 eq), o-isopropoxy-β- methylstyrene (1.5 eq), and p-toluenesulfonic acid (1.1 eq) in benzene was stirred at 40 ⁰C for 1 hour, The mixture was cooled to room temperature, the volatiles were removed under vacuum and the residue was washed with methanol. The green solid thus obtained was recrystallized from benzene//?-pentane to give H as a dark green, crystalline solid. [0074] Example 3a. RuCI₂(l,3-dimesϊtyi-4-methyl-imidazoiin-2-ylidene)(=CH-o- 'PrPh) (Hi)

6H).¹³C NMR (125 MHz, CD₂CI₂); δ 296.6 (m), 212.4, 152.5, 145.8, 140.4, 139.4, 139.3, 130.4, 130.1, 129.9, 129.6, 123.0, 122,6, 113.5, 75.6, 60.2 (br), 59.7 (br), 21.8, 21.5, 21.4, 19.9 (br). HRMS Calc'd for C₃₂H₄₀CI₂N₂ORu: 640.1562. Meas: 640.1578.

[0075] Example 3b, RuCI₂(4,4-dimethyl-l,3-dimesityl-imidazo[in-2- ylidene)(=CH-o-'PrPh) (H2)

IH),

=

213.3, 153.0, 146.4, 141.3, 139.0, 138.6, 130.7, 130.0, 129.3, 122.7, 122.5, 113.6, 75.4, 68.2 (br), 65.6 (br), 28.1, 21.8, 21.5, 21.4. HRMS Caic'd for C₃₃H₄₂CI₂N₂ORu:

654.1718. Meas: 654.1725.

[0076] Example 3c. RuCl₂(l,3-dϊmesϊtyl-4,5-dϊmethyHmldazolin-2- yIidene)(-CH-o-'PrPh) (H3)

6H), 0.81 (d, 3 = 6.5 Hz, 6H)-¹³C NMR (125 MHz, C₆D₆): δ 293.8, 213.4, 153.0, 146.4,

140.7, 138.7, 130.2, 129.9, 128.8, 122.8, 122.5, 113.6, 75.3, 62.4 (br), 21.8, 21.4, 13.9

(br). HRMS Calc'd for C₃₃H₄₂CI₂N₂ORu : 654.1718. Meas: 654.1738.

[0077] Example 3d. RuCl₂(l,3-dϊmesityl-4,4,5-trimethyl-ϊmidazolϊn-2- ylidene)(=CH-o-'PrPh) (H4) rocedure C. Stirred for 2.5 hr at room 60 °C. ¹H NMR (500 MHz, C₆D₆, ), 7.13-7.07 (m, 3H), 6.94 (br m, 3H), z, IH), 6.31 (d, 3 = 8.0 Hz, IH), 4.46 4.20 (br s, IH), 2.85-2.47 (m, 12H),

H), 1.28 (d, J = 6.1 Hz, 6H), 1.15 (br s, 3H), 0.88 (br s, 3H), 0.69 (br d, J = 6.9 Hz, 3H). ¹³C NMR (125 MHz, C₆D₆): δ 293.8

(m), 213.4 (br), 152.9, 146.5, 140.7, 138.7, 138.6, 130.9, 130.6, 130.3, 129.4, 122.7,

122.4, 113.6, 75.3, 71.0 (br), 68.4 (br), 25.1, 23.1 (br), 21.8, 21.5, 21.4, 12.1. HRMS

CaIc^ fOr C₃₄H₄₄CI₂N₂ORu: 668.1875. Meas: 668.1898.

[0078] Example 3e. RuCI₂[l,3-bis(2,6-difluorophenyl)-4,4,5,5-tetraniethyl- imidazolin-2-ylidene] ( =CH-o-'PrPh ) (H5)

A solution of l,3-bis(2,6-difluorophenyl)-4,4,5,5-tetramethyl- 4,5-dihydro-lH-imidazol-3-ium chloride (80 mg, 0.207 mmol) in benzene (3.5 ml) was added KHMDS (45 mg, 0.224 mmol), and the resulting solution was stirred at room temperature for 10 min. To this, RuCI₂(PCy₃)(=CH-o-iPrPh) (104 mg, 0.173 mmo!) was added, and the mixture was stirred for 18 hr at room temperature. After evaporation, the residue was purified by

column chromatography on TSI silica (eluent: π-pentane/di ethyl ether = 2/1 ~ 2/3) to give the titled compound as a green solid (56 mg, 0.084 mmol, Y =

48%).

¹H NMR (300 MHz, C₆D₆): δ 16.91 (s, IH), 7.11-7.05 (m, 3H), 6.68-6.54 (m, 6H), 6.36-6.33

(m, IH), 4.50 (sept, J = 6.2 Hz, IH), 1.42 (d, J = 6.2 Hz, 6H), 1.08 (s, 6H), 1.08 (s, 6H).

¹⁹F NMR (282 MHz, C₆D₆): δ -106.8. HRMS Calc'd for C₂₉H₃₀CI₂F₄N₂ORu : 670.0715. Meas:

670.0738.

[0079] Example 3f. RuCI_z[l_/3-bis(phenyi)-4,4,5,5-tetramethyl-imidazolin-2- yiidene](=CH-o-'PrPh) (H6)

Prepared according to procedure C. Stirred for 4 hours at RT. Crystals suitable for X-ray crystallography were grown at room temperature by slow diffusion of pentane into a δ Hz,

(t, J 6.2

6H). ¹³C NMR (125 MHz, C₆D₆): δ 211.0, 153.7, 144.7,

141.3, 139.5, 133.7, 131.8, 129.4, 128.9, 128.7, 128.5, 128.3, 122.6, 122.2, 113.6, 75.1, 71.3, 70.1, 22.4, 22.3. HRMS Calc'd TOr C₂₉H₃₄CI₂N₂ORu: 598.1092. Meas: 598.1070. X-Ray Structural Analysis of H6 is shown in Figure 13.

[0080] Example 3g, RuCI₂[l_f3-bis(o-toIyl)-4,4,5,5-tetramethyl-imidazolin-2- ylidene](s=CH-o-'PrPh) (H7) 3

),

10H), 1.04 (S, 2H), 0.76-0.70 (m, 6H).

¹³C NMR (125 MHz, C₆D₆): δ 214.0, 211.5, 153.1, 153.0, 145.8, 143.3, 143.2, 141.6, 140.8, 1403, 139.8, 137.3, 136.5, 136.0, 134.7, 134.4, 132.3, 132.2, 131.9, 129.6, 129.5, 129.4, 129.1, 128.9, 127.6, 127.3, 126.9, 126.6, 122.7, 122.6, 122.6, 122.5, 113.5, 75.2, 75.1, 72.3, 71.8, 71.7, 71.4, 24.9, 24.3, 24.1, 23.9, 22.7, 22.5, 22.4, 22.2, 22.1, 22.0, 20.3, 20.1, 19.7, 19.4, 19.3. HRMS Calc'd for C_3IH₃₈CI₂N₂ORu: 626.1405. Meas: 626.1427.

[0081] Example 3h. RuCI₂(i-Mesityl-4,4-dtmethyl-3-phenylimidazoIin-2- ylidene)(=CH-o-'PrPh) (HS) at RT. 16.48 (s, J = 0.6 IH), 4.90 (s, 6H), MHz, , 139.4,

138.8, 138.1, 136.5, 135.6, 130.1, 1230,0, 129.4, 128.9(0), 128.8(6), 122.9, 122.5, 113.4, 75.4, 66.0, 65.5, 27.8, 21.8, 21.5, 18.5. IR: 2967 (m), 1589 (m), 1572 (m), 1489 (m), 1472 (m), 1450 (m), 1380 (s), 1317 (m), 1286 (s), 1207 (m), 1179 (m), 1154 (m), 1113 (s), 1031 (w), 931 (m), 877 (w), 805 (w), 770 (w), 754 (m), 699 (m) cm^"1. HRMS Calc'd for C₃₄H₄₄CI₂N₂ORu: 612.1249. Meas: 612. 1229.

[0082] Example 4. Standard Activity Tests of the Ruthenium catalysts (see the catalysts in Example 3) for Ring Closing Metathesis (RCM)

[0083] Ail test were performed according to the experimental procedure described by Ritter et al. (see Ritter, T.; Hejl, A.; Wenzel, A.; Funk, T. W.; Grubbs, R. H., Organometallics, 2006, 25, 5740.)

[0084] Preparation of a Stock Solution for the Ring Closing Metathesis (RCM) Tests: Inside a glove box, a volumetric flask is charged with the ruthenium complex H or P (0.016 mmol) and CD₂CI₂ or C₆D₆ was added to prepare 1.0 ml of stock solution (0.016 M). [0085] Selected Activity Test Results: Complexes PO, P2, P4, HO₇ Hl, H2, H4 were tested against. Catalysts PO and HO are described in Schoil, M. ; Ding, S. ; Lee, C. W.; Grubbs, R, H. Org. Lett. 1999, 1, 953-956; Schwab, P.; Grubbs, R. H.; Ziller, 3. W. J, Am. Chem. Soc.1996, 118, 100-110; and Schwab, P.; France, M. B.; Ziller, 3. W.; Grubbs, R. H. Angew. Chem., Int. Ed. 1995, 34, 2039-2041. All complexes P and H efficiently catalyzed the RCM reactions of diethyl diallyl malonate (R7, Figure 1) and diethyl allylmethallylmalonate (R9, Figure 2). For complexes P, the substitution pattern does not seem to have any influence on the course of the reaction under the conditions tested. For catalysts H, the backbone substitution seems to decrease the initiation rate at 30 ⁰C.

^P0 HO

[0086] Example 4a. RCM of Diethyl diallylmalonate (R7) : An NMR tube with a screw- cap septum top was charged inside a glovebox with catalyst stock solution (50 μL, 0.80 μmoi, 1.0 mol%) and CD₂Cl₂ or C₆D₆ (750 μL). The sample was equilibrated at 30 (CD₂Ci₂) or 60 ⁰C (C₆D₆) in the NMR probe before R7 (19.3 μL, 19.2 mg, 0.080 mmol, 0.1 M) was added via syringe. Data points were collected over an appropriate period of time using the Varian array function. The conversion to R8 was determined by comparing the ratio of the integrals of the methylene protons in the starting material, δ 2.61 (dt), with those in the product, δ 2.98 (s). At 60 ⁰C, the differences between catalysts of type H are minimal, results are shown on Figure 1.

[0087] Example 4b. RCM of Diethyl allylmethallylmalonate (R9): An NMR tube with a screw-cap septum top was charged inside a glovebox with catalyst stock solution (50 μl_, 0.80 μmol, 1 mol%) and CD₂CI₂ or C₆D₆ (750 μL). The sample was equilibrated at 30 (CD₂CI₂) or 60 ⁰C (C₆D₆) in the NMR probe before R9 (20.5 μL, 20.4 mg, 0.080 mmoi, 0.1 M) was added via syringe. Data points were collected over an appropriate period of time using the Varian array function. The conversion to RlO was determined by comparing the ratio of the integrals of the methylene protons in the starting material, δ 2.67 (s), 2.64 (dt), with those in the product, δ 2,93 (s), 2.88 (m). Results are shown on Figure 2.

[0088] Example 5; Standard Activity Tests of the Ruthenium catalysts H6 and H7 (see H6 and H7 in Example 3f and 3g) for Ring Closing Metathesis (RCM) [0089] All the test were performed according to the experimental procedure described by Ritter et a!, (see Ritter, T.; Hejl, A.; Wenzel, A. ; Funk, T. W.; Grubbs, R. H., Organometallics, 2006, 25, 5740.)

[0090] Preparation of a Stock Soiution for the Ring Closing Metathesis (RCM) Tests: Inside a glove box, a volumetric flask is charged with H6 (9.6 mg, 0.016 mmol) and CD₂CI₂ or C₆D₆ was added to prepare 1.0 ml of stock solution A (0.016 M). Stock solution B was prepared in the same manner using H7 (10.0 mg, 0.016 mmol).

[0091] Activity test results: The complexes H6 and H7 efficiently catalyzed the RCM reactions of diethyl diatlyi malonate (R7, Figure 3) and diethyl allylmethallylmalonate (R9, Figure 4) although there was a prolonged induction period at 30 ⁰C compared to the known ruthenium complex HO.

[0092] Example 5a. RCM of Diethyl diaSlylmalonate (R7): An NMR tube with a screw- cap septum top was charged inside a glovebox with catalyst stock solution (SO μL, 0.80 μmoi, 1.0 rnol%) and CD₂CI₂ or C₆D₆ (750 μL). The sample was equilibrated at 30 (CD₂CI₂) or 60 ⁰C (C₆D₆) in the NMR probe before R7 (19.3 μL, 19.2 mg, 0.080 mmol, 0.1 M) was added via syringe. Data points were collected over an appropriate period of time using the Varian array function. The conversion to R8 was determined by comparing the ratio of the integrals of the methylene protons in the starting material, δ 2.61 (dt), with those in the product, δ 2.98 (s). Results are shown on Figure 3.

[0093] Example 5b. RCM of Diethyl aiiylmethallylmalonate (R9, Figure 4) : An

NMR tube with a screw-cap septum top was charged inside a glovebox with catalyst stock solution (50 μL, 0.80 μmol, 1 mol%) and CD₂CI₂ or C₆D₆ (750 μL). The sample was equilibrated at 30 (CD₂CI₂) or 60 °C (C₆D₆) in the NMR probe before R9 (20.5 μl_, 20.4 mg, 0.080 mmoS, 0.1 M) was added via syringe. Data points were collected over an appropriate period of time using the Varian array function. The conversion to RlO was determined by comparing the ratio of the integrals of the methylene protons in the starting material, δ 2.67 (s), 2.64 (dt), with those in the product, δ 2.93 (s), 2.88 (m).

[0094] At 60 °C, both H6 and H7 initiated fast and reached 90% conversion in less than 3 minutes for RCM of R7, and less than 20 minutes for RCM of R9 (Figure 5). [0095] Example 5c. RCM of Diethyl dimethallylmalonate fRll) An NMR tube with a screw-cap septum top was charged inside a glovebox with catalyst stock solution (50 μL_r 0.80 μmol, 1 mo!% or 250 μL, 4.0 μmoi, 5 mol%) and CD₂CI₂ or C₆D₆ (750 or 550 μL respectively). The sample was equilibrated at 30 (CD₂Cl₂) or 60 ⁰C (C₆D₆) in an oil bath, and RIl (21.6 μL, 21.5 mg, 0.080 mmol, 0.1 M) was added via syringe. Data points were collected over an appropriate period of time. The conversion to R12 was determined by comparing the ratio of the integrals of the methylene protons in the starting material, δ 2.71 (s) with those in the product, δ 2.89 (s).

[0096] Complexes H6 and H7 proved to be very efficient catalysts for tetrasubstituted olefin-forming RCM reactions, superior to the known ruthenium complex HO as illustrated in Figure 6. Notably, the complex H6 could catalyze this challenging reaction to give 85% conversion in 20 hours with 1 mol% of the catalyst loading. At 60 ⁰C with 5 mol% of H6, the same reaction went completion in 20 minutes.

[0097] Example 6: Comparison of Standard Activity Tests of the Ruthenium tetrasubstituted NHC complex H6 (see Example 3f) to the Ruthenium gem di-substituted NHC complex H8 (see Example 3h) for Ring Closing Metathesis (RCM), Cross Metathesis (CM) and Ring-Opening Metathesis Polymerization (ROMP) reactions. [0098] Example 6a. RCM Reactions: All tests were performed according to the experimental procedure described by Ritter et al. (see Ritter, T.; Heji, A.; Wenzel, A.; Funk, T. W. ; Grubbs, R. H., Organometallics, 2006, 25, 5740.) See Figure 7a, 7b and 7c.

CD₂CI₂, 30⁰C C₆D₆, 60^uC

(%)

EtO₂C CO₂Et EtO₂C CO₂Et Catalyst Ytefd catalyst (1 mo! %)

1) solvent, temperature O HO 99% {30 miπ) v-_. — / H6 95% (2h) 98% (5 mm)

R7 R8 H8 95% (4h) 95% (10 min)

EtO₂C CO₂Et EtO₂C CO₂Et

HO 6% (96h) 30% (24 min) catalyst (5 mol %) H6 95% (4h) 98% {20 min)

3) X ^?~\ h P=^r ssoollvveenntt,, t teemmppeerraattuurree _y H O H8 no reaction 55% (31 h)

_R11 R12

Scheme 3. RCM Reactions with backbone substituted catalysts ^a ^a Reactions were performed in NMR tubes with closed caps and conversions were determined by NMR. [0099] Example 6b, CM Reactions (see figure 81

catalyst (25 mol %)

CO₂OI₂ (O-Z M), 25 °C

(1) Ph" AcO- -OAc

26 27 28 (ez;

HO 72% (10/1) H6 78% (8/1) HS 57% (4/1) %) 30 ⁰C

2S 30

HO 99% (< 5 mm)

Scheme 4. Cross- metathesis³ and ROMP^δ with backbone substituted catalysts ^a Conversion and E/Z ratio was determined by GC analysis. b Reactions were performed in NMR tubes with closed caps and conversions were determined by NMR

[0100] Example 6c. ROMP of Cyclooctadiene (see Figure 9) [0101] Example 7: The initiation kinetics studies of compound H6 (see Example 3f).

The Eyring plot is shown on Figure 10.

£0102] The initiation kinetics studies of compound H6 were conducted according to literature procedures, (see Ritter, T.; Hejl, A.; Wenzel, A.; Funk, T. W.; Grubbs, R, H., Orgaπometallics, 2006, 25, 5740.)

(303 K) H6 HO

ΔH* (kcal/mol) 11.9 (± 1.7) 15.2 (± 0.8)

ΔS^* (e.u.) -30 (± 6) -19 (± 3)

AG* (kcat/moi) 21.0 (± 0.1) 20.7 (± 0.01) kinit 47 x 10 -4 67 x 10^"

[0103] Example 8: Ring-closing metathesis using low catalysts loadings.

[0104] Example 8a. HO, H2, H3, and H4 have been tested in the RCM of diethyl diallylmalonate R7 using 15 ppm of catalyst (see Figure 11).

[0105] Example 8b. H7 and H9 have been tested in the RCM of diethyl diallylmalonate

R7 using 15 ppm of catalyst (see Figure 12). Under those conditions, H7 leads to higher yields of R8.

[0106] Example 8c. HO, H4, H6, H7 and H9 have been tested in the RCM of R9 using

200 ppm of catalyst (Scheme 5).

(%)

H6 31

Scheme 5

Claims

What is claimed is:

1. An imidazolinium sa!t of formula (I):

X wherein: a) R¹ and R⁴ are methyi; and

R² and R³ are independently selected from methyl, ethyl, or allyl, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring;

R⁵ and R⁶ are each independently a C₁-C₁₀ alky!, cycloaikyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II);

wherein, n ranges from 1 to 3; with the proviso that only one of R⁵ or R⁶ may be a linear alky! group having 3 or less carbons;

R⁷ is independently selected from hydrogen, Ci-C₁₀ alkyl, Cj-C₁₀ alkoxy, aryl, aralkyl, and one or more functional groups;

R⁸ and R⁹ are independently selected from hydrogen, C₁-C₁₀ alkyl, fluoride or chloride; with the proviso that R⁸ and R⁹ are not C₁-C₁₀ alkyl at the same time; and, wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; or, b) R¹ is methyi; R⁴ is H;

R² and R³ are independently selected from methyl, ethyl, ally!, or isopropyl, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring; with the proviso that R² and R³ are not both isopropyl at the same time;

R⁵ and R⁶ are each independently a C₁-C₁₀ alkyi, cycloalkyl, a fused or bridged ring, aralkyi, or a group having the structure of formula (II);

wherein, n ranges from 1 to 3; with the proviso that only one of R⁵ or R⁶ may be a linear alkyl group having 3 or less carbons;

R⁷ is independently selected from hydrogen, C₁-C₁₀ alkyl, C₁-Ci₀ alkoxy, aryi, aralkyi, and one or more functional groups ;

R⁸ and R⁹ are independently selected from hydrogen, CrC₁₀ alkyt, fluoride or chloride; and, wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; and,

X^" is an anion for the imidazolinium salt.

2. The imidazolinium salt of claim 1, wherein:

R¹ and R⁴ are methyl;

R² and R³ are methyl, or R² and R³ together with the carbons carrying them form a fused 6-membered carbocylic ring;

R⁵ and R⁶ are independently selected from the group consisting of isopropyl, tertbutyl, neopentyl, phenyl, or a group a group having the structure of formula (II):

wherein n ranges from 1 to 3;

R⁷ is independently selected from hydrogen, C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, aryl, aralkyl, and one or more functional groups; and,

R⁸ and R⁹ are independently selected from hydrogen, C₁-C₁₀ alkyl, fluoride or chloride; with the proviso that R⁸ and R⁹ are not C₁-C₁₀ alkyl at the same time.

3. The imidazolinium salt of claim 2, wherein: R² and R³ are methyl;

R⁵ and R⁶ are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyl, o-difluorophenyl, o-dichlorophenyl or o-isopropylphenyi; and,

X is chloride, bromide, iodide, tetrafluroborate (BF₄) or trifluoroacetate (CF₃COO).

4, The imtdazoiinium salt of claim 1, wherein: R¹ is methyl;

R⁴ is H;

R⁵ and R⁶ are independently selected from isopropyl, tertbutyl, neopentyl, phenyl, or a group having the structure of formula (II):

wherein n ranges from 1 to 3; R⁷ is independently selected from hydrogen, CrCi₀ alkyl, C₁-C₁₀ alkoxy, aryl, araikyl, and one or more functional groups; and,

R⁸ and R⁹ are independently selected from hydrogen, CrCi₀ alkyl, fluoride or chloride.

5. The imidazoiinium salt of claim 4, wherein:

R^z and R³ are methyl, or R² and R³ together with the carbons carrying them form a fused 6- membered carbocylic ring;

R⁵ and R⁶ are independently selected from phenyl, mesityl, o-toiyl, rn-tolyl, p-tolyl, o-difluorophenyl, o-dichloropheynl or o-isopropylphenyi; and,

X^" is chloride, tetraf!uroborate(BF₄) or trifluoroacetate (CF₃COO).

6. The /V-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of formula (III):

wherein:

X¹ and X² are independently anionic ligands;

R¹⁰ and R¹¹ are each independently hydrogen or a substituted or unsubstituted substituent selected from CrC₂₀ alkyl, C₂-C₂O alkenyl, C₂-C₂₀ alkynyl, aryl, CrC₂O carboxylate, Ci-C₂₀ alkoxy, C₂-C₂₀ alkenyioxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, CrC₂₀ alkylthio, C₁-C₂₀ alkylsuifonyl or C_x-C₂₀ alkylsulfinyl; or R¹⁰ and R¹¹ may optionally be linked together to form a cyclic structure via one of the listed substituents; m is 1 or 2, wherein, when m is 1, L is a neutral 2-electron donor ligand and may optionally be linked to R¹¹ forming a chelating carbene ligand; and, when m is 2, L is a heteroarene ligand; and

NHC is an N-heterocyclic carbene (NHC) iigand of formula (IV):

a) R¹ and R⁴ are methyl; and

R² and R³ are independently selected from methyl, ethyl, and ally!, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocyiic ring;

R⁵ and R⁶ are each independently a C₁-Ci₀ alky!, cycloalkyi, a fused or bridged ring, aralkyl, or a group having the structure of formula (II):

R⁷ is independently selected from hydrogen, C₁-Ci₀ alkyl, C₁-C₁₀ alkoxy, aryl, aralkyl, and one or more functional groups;

R⁸ and R⁹ are independently selected from hydrogen, C₁-C₁₀ alkyl, fluoride, or chloride; with the proviso that R⁸ and R⁹ are not C₁-C₁₀ alkyl at the same time; and, wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; b) R¹ is methyl;

R⁴ is H;

R² and R³ are independently selected from methyl, ethyl, allyl and isopropyl, or R² and R³ together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocyiic ring; with the proviso that R² and R³ are not both isopropyl at the same time; and R⁵ and R⁶ are each independently a C₁-Ci₀ alkyl, cydoalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II):

R⁷ is independently selected from hydrogen, CrCi₀ alkyl, C₁-Ci₀ alkoxy, aryl, aralkyl, and one or more functional groups;

R⁸ and R⁹ are hydrogen, C₁-Ci₀ alkyl, fluoride or chloride; and, wherein R² and/or R³ may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹; or, c) R¹ and R^z are C₁-Ci₀ alkyl, or together form a cyclic structure;

R³ and R⁴ are H;

R⁵ and R⁶ are each independently a CrC₁₀ alkyl, cycloaikyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II):

wherein, n ranges from 1 to 3; with the proviso that only one of R⁵ or R⁶ may be a linear alkyl group having 3 or less carbons; R⁷ is independently selected from hydrogen, Ci-Ci₀ alkyl, C₁-C₁₀ alkoxy, ary!, aralkyl, and one or more functional groups;

R⁸ and R⁹ are hydrogen, CrCi₀ alkyl, fluoride or chloride; and, wherein R¹ and/or R² may form a cyclic structure with one or both of R⁵ and R⁶, or through one or more links with at least one of R⁷, R⁸ and R⁹.

7. The ^-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6, wherein:

R¹ and R⁴ are methyl;

R² and R³ are methyl, or R² and R³ together with the carbons carrying them form a fused 6-membered carbocylic ring; and,

R^s and R⁶ are independently selected from isopropyl, tertbutyl, neopentyl, phenyl, or a group having the structure of formula (II):

wherein, n ranges from 1 to 3;

R⁷ is methyl, fluoride or chloride; and,

R⁸ and R⁹ are as defined in claim 6.

8. The Λ/-heterocyc!ic carbene (NHC) ruthenium olefin metathesis catalyst of ciaim 7, wherein :

R² and R³ are methyl; and

R⁵ and R⁶ are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyi, o-difluorophenyl, o-dichloropheynl or o-isopropylphenyl.

9. The /V-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6, wherein:

R¹ is methyl; R⁴ is H;

R² and R³ are methyl, or R² and R³ together with the carbons carrying them form a fused 6-membered carbocylic ring; and

wherein, n ranges from 1 to 3;

R⁷ is methyl, fluoride or chloride; and,

R⁸ and R⁹ are as defined in claim 6.

10, The N- heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 9, wherein:

R⁵ and R⁶ are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyl, o-difluorophenyl, o-dichloropheynl or o-isopropyiphenyl.

11. The /V-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6, 7, 8, 9 or 10, wherein:

X¹ and X² are halide, or a substituted or unsubstituted group selected from benzoate, Ci-C₅ carboxylate, Ci-C₅ alkyl, phenoxy, C₁-C₅ alkoxy, C₁-C₅ alkylthio, aryt, or C₁-C₅ alkyl sulfonate;

R¹⁰ is hydrogen, Ci-C₅ alkyl or aryl;

R¹¹ is a substituted or unsubstituted group selected from C₁-C₂O alkyl, C₂-C₂O alkeπyl, or aryl; m is 1; and, L is selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonϊte, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, or thioether, or is linked to R¹¹ forming a chelating carbene ligand,

12. The N- heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 11, wherein:

X¹ and X² are each haϋde, CF₃ CO₂, CH₃,CO₂, CFH₂ CO₂, (CH₃)₃ CO, (CF₃)₂ (CH₃)CO, (CF₃)(CH₃)₂CO, PhO, MeO, EtO, tosyiate, mesylate, or trifluoromethanesulfonate;

R¹⁰ is hydrogen, C₁-C₅ aikyl or aryl;

R¹¹ is a substituted or unsubstituted group selected from the group consisting of C₁-C₂₀ aikyl, C₂-C₂₀ alkenyl, and aryl; m is V₁ and,

L is a phosphine of the formula PR'R"R"', where R', R", and R'" are each independently aryl, C₁-C₁₀ aikyl, or C₃-C₆ cycloalkyl, or is linked to R¹¹ forming a chelating carbene ligand.

13. The N- heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 12, wherein:

X¹ and X² are each chloride; R¹⁰ is hydrogen;

R¹¹ is phenyl, vinyl or -C=C(CH₃)₂; m is 1; and

L is selected from P(cyclohexyl)₃, P(cyclopentyl)₃, P(isopropyl)₃, or P(phenyl)₃, or is linked to R¹¹ forming a chelating carbene ligand.

14. The Λ/-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6, wherein the catalyst of formula (III) has the structure of formula (V):

wherein, NHC is an ^-heterocyclic carbene (NHC) ligand of formula (IV), as defined in claim 6;

Y is a heteroatom selected from oxygen, sulfur, nitrogen, or phosphorus;

X¹ and X² are independently anionic ligands;

Z is selected from hydrogen, alkyl, alkenyi, aJkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryioxy, functionalized alkyl, or functionalized aryl, wherein the functional group(s) may independently be selected from alkoxy, aryioxy, halogen, carbonyl, carboxylic acid, ketone, aldehyde, nitrate, nitrile, nitro, cyano, isocyanate, hydroxyf, ester, ether, amine, imine, amide, sulfide, sulfonyl, sulfinyi, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or combinations thereof; each optionally substituted with an alkyl, halogen, alkoxy, aryl, aryioxy, or heteroaryl moiety;

R^a, R^b, R^c, and R^d are independently selected from hydrogen, halogen, alkyl, alkenyi, alkynyl, aryl, heteroary), alkoxy, alkenyloxy, alkynyloxy, aryioxy, functionalized alkyl, or functionalized aryl, wherein the functional group(s) may independently be selected from alkoxy, aryioxy, halogen, carbonyl, carboxylic acid, ketone, aldehyde, nitrate, nitrile, nitro, cyano, isocyanate, hydroxy), ester, ether, amine, imine, amide, sulfide, sulfonyl, sulfinyi, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or combinations thereof; each optionally substituted with an alkyl, halogen, alkoxy, aryl, aryioxy, or heteroaryl moiety, wherein any two or more of R^a, R^b, R^c, and R^d may be independently linked through hydrocarbon or functionalized hydrocarbon groups forming an aliphatic or aromatic ring.

15. The /V- heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 13, wherein the catalyst of formula (III) is selected from:

16. The Λ/-heterocyciic carbene (NHC) ruthenium olefin metathesis catalyst of claim 11, wherein the catalyst of formula (III) is selected from:

17. The /V-heterocyc!ic carbene (NHC) ruthenium olefin metathesis catalyst of claim 13, wherein L is selected from P(cyclohexyl)₃, P(cyclopentyl)₃, P(isopropyl)₃, or P(phenyl)₃,

18. The Λ/-heterocyciic carbene (NHC) ruthenium olefin metathesis catalyst of claim 11, wherein L is selected from P(cyclohexyl)₃, P(cyclopentyl)₃, P(isopropyl)₃, or P(phenyl)₃.

19. A ring-closing metathesis method for preparing a tetrasubstituted cyclic olefin comprising : contacting an olefinic compound having at least two terminal olefins which are substituted at the beta-carbon of each terminal olefin with an Λ/-heterocydic carbene (NHC) ruthenium olefin metathesis catalyst of claims 6, 7, 8, 9 or 10 under metathesis conditions to form a cyclic tetra-substituted olefin.

20. The method of claim 12 wherein the catalyst is present in an amount ranging from about 25 ppm to about 10 mol%.

21. An olefin metathesis reaction comprising the step of: contacting an olefin with an Λ/-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6, 7, 8, 9 or 10 under metathesis conditions.

22. A cross-metathesis reaction comprising the step of contacting an olefin and a tri- substituted olefin or a di-substituted olefin having further substitution at the allylic carbon with an Λ/-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6, 7, 8, 9 or 10 under metathesis conditions.