Synthesis and characterization of Ru alkylidene complexes

Abstract

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis of olefins and olefin compounds. The invention has utility in the fields of catalysts, organic synthesis, polymer chemistry, and industrial and fine chemicals industry.

Claims

1. A method of synthesizing an olefin metathesis catalyst represented by the structure of Formula (C) ##STR00701## the method comprising contacting an olefin metathesis catalyst represented by the structure of Formula (IVa) ##STR00702## with a N-Heterocyclic Carbene ligand of formula ##STR00703## at, wherein: X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —NRC.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted C.sub.5-C.sub.24 aryl, or substituted C.sub.5-C.sub.24 aryl; generally R.sup.5 and R.sup.6 are independently substituted C.sub.5-C.sub.24 aryl with one to three unsubstituted (C.sub.1-C.sub.6 alkyl) groups or substituted (C.sub.1-C.sub.6 alkyl) groups.

2. The method according to claim 1, wherein: R.sup.1 is morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; R.sup.2 is phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; and R.sup.3 is phenyl or morpholino; X.sup.1 is Cl; X.sup.2 is Cl; and R.sup.5 and R.sup.6 are independently 2,4,6-trimethyl-phenyl, or 2,6-di-iso-propylphenyl.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C940.

(2) FIG. 2. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C958.

(3) FIG. 3. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C852.

(4) FIG. 4. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C803.

(5) FIG. 5. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C850.

(6) FIG. 6. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C825.

(7) FIG. 7. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C832.

(8) FIG. 8. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C865.

(9) FIG. 9. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C829.

(10) FIG. 10. Vinyl ether quenching experiments for catalysts: C849, C865, C825, C850, C852, and C832.

(11) FIG. 11. Vinyl ether quenching experiments for catalysts: C831, C840, C849, and C858.

(12) FIG. 12. Vinyl ether quenching experiments for catalysts: C848, C852, C855, C858.

DETAILED DESCRIPTION

(13) Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, or the like, as such can vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting.

(14) As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an olefin” includes a single olefin as well as a combination or mixture of two or more olefins, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

(15) As used in the specification and the appended claims, the terms “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion.

(16) In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

(17) The term “alkyl” as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing generally 1 to 30 carbon atoms, typically 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, 1-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms. The term “substituted alkyl” refers to alkyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.

(18) The term “alkylene” as used herein refers to a divalent linear, branched, or cyclic alkyl group, where “alkyl” is as defined above.

(19) The term “alkenyl” as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to 30 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Typically alkenyl groups herein contain 2 to 12 carbon atoms. The term “lower alkenyl” intends an alkenyl group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic alkenyl group, typically having 5 to 8 carbon atoms. The term “substituted alkenyl” refers to alkenyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively. The term “alkenyl” is used interchangeably with the term “olefin” herein.

(20) The term “alkenylene” as used herein refers to a divalent linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

(21) The term “alkynyl” as used herein refers to a linear or branched hydrocarbon group of 2 to 30 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Typical alkynyl groups described herein contain 2 to 12 carbon atoms. The term “lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to alkynyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.

(22) The term “alkoxy” as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group can be represented as —O-alkyl where alkyl is as defined above. A “lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

(23) The term “aryl” as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Generally aryl groups contain 5 to 30 carbon atoms, and typically aryl groups contain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups. The terms “heteroatom-containing aryl” and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.

(24) The term “aryloxy” as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above. An “aryloxy” group can be represented as —O-aryl where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

(25) The term “alkaryl” refers to an aryl group with an alkyl substituent, and the term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above. Generally alkaryl and aralkyl groups contain 6 to 30 carbon atoms, and typically alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula —OR wherein R is alkaryl or aralkyl, respectively, as defined herein.

(26) The term “acyl” refers to substituents having the formula —(CO)-alkyl, —(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers to substituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or —O(CO)-aralkyl, wherein “alkyl,” “aryl,” and “aralkyl” are as defined above.

(27) The terms “cyclic” and “ring” refer to moieties which are saturated or have unsaturations and are non-aromatic or are aromatic and that are optionally substituted and/or heteroatom containing, and that can be monocyclic, bicyclic, or polycyclic.

(28) The term “saturated N-heterocycle” as used herein refers to a heteroatom-containing cyclic group, which is saturated and is attached to the rest of the molecule by a nitrogen (N) atom. The saturated N-heterocycle moiety contains rings wherein one or more carbon(s) has been replaced by a heteroatom, such as: N, S or O. Unsubstituted “saturated N-heterocycle” groups include pyrrolidino, morpholino, piperazino, piperidino, thiomorpholino, etc. Substituted “saturated N-heterocycle” groups include 1-methyl-piperazino, N-acetyl-piperazino, N-ethylcarboxylate-piperazino, etc.

(29) The terms “halo,” “halogen,” and “halide” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

(30) The term “hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 to 30 carbon atoms, typically containing 1 to 24 carbon atoms, specifically containing 1 to 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl” intends a hydrocarbyl group of 1 to 6 carbon atoms, typically 1 to 4 carbon atoms, and the term “hydrocarbylene” intends a divalent hydrocarbyl moiety containing 1 to 30 carbon atoms, typically 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term “lower hydrocarbylene” intends a hydrocarbylene group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbyl substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, “substituted hydrocarbylene” refers to hydrocarbylene substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbylene” and “heterohydrocarbylene” refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.

(31) The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is heteroatom-containing, the terms “heteroaryl” and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like. It should be noted that a “heterocyclic” group or compound is optionally aromatic, and further that “heterocycles” can be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.” Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.

(32) By “Grubbs-Hoveyda ligands,” is meant benzylidene ligands having a chelating alkyloxy group attached to the benzene ring at the ortho position.

(33) Examples of —NH(C.sub.1-C.sub.24 alkyl) groups include —NHMe (e.g., methylamino), —NHEt (e.g., ethylamine), —NH(i-Pr) (e.g., iso-propylamino), etc.

(34) Examples of —N(C.sub.1-C.sub.24 alkyl).sub.2 groups include —N(Me).sub.2 (e.g., dimethylamino), —N(Et).sub.2 (e.g., diethylamino), —N(i-Pr).sub.2 (e.g., di-iso-propylamino), etc.

(35) Examples of —NH(C.sub.5-C.sub.24 aryl) groups include —NH(C.sub.6H.sub.5) (e.g., phenylamino), etc.

(36) Examples of —N(C.sub.5-C.sub.24 aryl).sub.2 groups include —N(C.sub.6H.sub.5).sub.2 (e.g., diphenylamino), etc.

(37) Examples of —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) groups include —NMe(C.sub.6H.sub.5) (e.g., phenylmethylamino), etc.

(38) Examples of —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2 groups include —N[(CH.sub.2)(C.sub.6H.sub.5)].sub.2 (e.g., di-benzyl-amino), etc.

(39) By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy, C.sub.2-C.sub.24 alkenyloxy, C.sub.2-C.sub.24 alkynyloxy, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy, C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2-C.sub.24 alkylcarbonyl (—CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C.sub.2-C.sub.24 alkylcarbonyloxy (—O—CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyloxy (—O—CO-aryl)), C.sub.2-C.sub.24 alkoxycarbonyl (—(CO)—O-alkyl), C.sub.6-C.sub.24 aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X is halo), C.sub.2-C.sub.24 alkylcarbonato (—O—(CO)—O-alkyl), C.sub.6-C.sub.24 arylcarbonato (—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO—), carbamoyl (—(CO)—NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl (—(CO)—NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl (—(CO)—N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl (—(CO)—NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl (—(CO)—N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl (—(CO)—N(C.sub.5-C.sub.24 aryl).sub.2), di-N—(C.sub.1-C.sub.24 alkyl), N—(C.sub.5-C.sub.24 aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl (—(CS)—NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl (—(CS)—N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl (—(CS)—N(C.sub.5-C.sub.24 aryl).sub.2), di-N—(C.sub.1-C.sub.24 alkyl), N—(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl, carbamido (—NH—(CO)—NH.sub.2), cyano(—C≡N), cyanato (—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted amino, di-(C.sub.1-C.sub.24 alkyl)-substituted amino, mono-(C.sub.5-C.sub.24 aryl)-substituted amino, di-(C.sub.5-C.sub.24 aryl)-substituted amino, (C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl)-substituted amino, C.sub.2-C.sub.24 alkylamido (—NH—(CO)-alkyl), C.sub.6-C.sub.24 arylamido (—NH—(CO)-aryl), imino (—CR═NH where R=hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (—CR═N(alkyl), where R=hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), arylimino (—CR═N(aryl), where R=hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), nitro (—NO.sub.2), nitroso (—NO), sulfo (—SO.sub.2—OH), sulfonato (—SO.sub.2—O—), C.sub.1-C.sub.24 alkylsulfanyl (—S-alkyl; also termed “alkylthio”), C.sub.5-C.sub.24 arylsulfanyl (—S-aryl; also termed “arylthio”), C.sub.1-C.sub.24 alkylsulfinyl (—(SO)-alkyl), C.sub.5-C.sub.24 arylsulfinyl (—(SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl (—SO.sub.2-alkyl), C.sub.1-C.sub.24 monoalkylaminosulfonyl —SO.sub.2—N(H) alkyl), C.sub.1-C.sub.24 dialkylaminosulfonyl —SO.sub.2—N(alkyl).sub.2, C.sub.5-C.sub.24 arylsulfonyl (—SO.sub.2-aryl), boryl (—BH.sub.2), borono (—B(OH).sub.2), boronato (—B(OR).sub.2 where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH).sub.2), phosphonato (—P(O)(O.sup.−).sub.2), phosphinato (—P(O)(O.sup.−)), phospho (—PO.sub.2), and phosphino (—PH.sub.2); and the hydrocarbyl moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl, more preferably C.sub.1-C.sub.6 alkyl), C.sub.2-C.sub.24 alkenyl (preferably C.sub.2-C.sub.12 alkenyl, more preferably C.sub.2-C.sub.6 alkenyl), C.sub.2-C.sub.24 alkynyl (preferably C.sub.2-C.sub.12 alkynyl, more preferably C.sub.2-C.sub.6 alkynyl), C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.14 aryl), C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl).

(40) By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove. The term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.

(41) In addition, the aforementioned functional groups can, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above. Analogously, the above-mentioned hydrocarbyl moieties can be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

(42) “Optional” or “optionally” means that the subsequently described circumstance can or cannot occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent can or cannot be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Olefin Metathesis Catalysts

(43) In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (VI):

(44) ##STR00008##
wherein:

(45) X.sup.1 and X.sup.2 are independently anionic ligands; generally X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X.sup.1 and X.sup.2 are independently Cl, Br, I or F;

(46) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene) (C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(47) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2; and

(48) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle.

(49) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (VI), wherein X.sup.1 is Cl; X.sup.2 is Cl; R.sup.1 is morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; R.sup.2 is phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; and R.sup.3 is phenyl or morpholino.

(50) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (VII):

(51) ##STR00009##
wherein:

(52) X.sup.1 and X.sup.2 are independently anionic ligands; generally X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X.sup.1 and X.sup.2 are independently Cl, Br, I or F;

(53) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(54) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(55) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or substituted saturated N-heterocycle;

(56) Y is CR.sup.4 or N; generally Y is N;

(57) R.sup.4 is hydrogen, unsubstituted (C.sub.1-C.sub.12 alkyl), or substituted (C.sub.1-C.sub.12 alkyl);

(58) R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted (C.sub.5-C.sub.24 aryl), or substituted (C.sub.5-C.sub.24 aryl); generally R.sup.5 and R.sup.6 are independently substituted (C.sub.5-C.sub.24 aryl);

(59) Q is a two-atom linkage represented by structures —[CR.sup.7R.sup.8].sub.s—[CR.sup.9R.sup.10].sub.t— or —[CR.sup.11═CR.sup.12]—;

(60) R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are independently hydrogen, unsubstituted (C.sub.1-C.sub.24 alkyl), substituted (C.sub.1-C.sub.24 alkyl), unsubstituted (C.sub.5-C.sub.24 aryl), or substituted (C.sub.1-C.sub.24 aryl); or any two of R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure; generally R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are independently hydrogen, unsubstituted (C.sub.1-C.sub.12 alkyl), substituted (C.sub.1-C.sub.12 alkyl), unsubstituted (C.sub.5-C.sub.14 aryl) or substituted (C.sub.5-C.sub.14 aryl);

(61) R.sup.11 and R.sup.12 are independently hydrogen, unsubstituted (C.sub.1-C.sub.24 alkyl), substituted (C.sub.1-C.sub.24 alkyl), unsubstituted (C.sub.5-C.sub.24 aryl), or substituted (C.sub.5-C.sub.24 aryl); or R.sup.11 and R.sup.12 are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure; and

(62) “s” and “t” are independently 1 or 2; generally “s” and “t” are independently 1.

(63) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (VIII):

(64) ##STR00010##
wherein:

(65) X.sup.1 and X.sup.2 are independently anionic ligands; generally X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X.sup.1 and X.sup.2 are independently Cl, Br, I or F;

(66) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(67) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(68) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle; and

(69) R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted C.sub.5-C.sub.24 aryl, or substituted C.sub.5-C.sub.24 aryl; generally R.sup.5 and R.sup.6 are independently substituted C.sub.5-C.sub.24 aryl with one to three unsubstituted (C.sub.1-C.sub.6 alkyl) groups or substituted (C.sub.1-C.sub.6 alkyl) groups.

(70) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (VIII), wherein X.sup.1 is Cl; X.sup.2 is Cl; R.sup.1 is morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; R.sup.2 is phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; R.sup.3 is phenyl or morpholino; and R.sup.5 and R.sup.6 are independently 2,4,6-trimethyl-phenyl (e.g., mesityl or Mes), 2,6-di-iso-propylphenyl (e.g., DIPP or DiPP), 2-iso-propylphenyl (e.g., IPP or Ipp), or 2-methyl-6-iso-propylphenyl (e.g., MIPP or Mipp or MiPP).

(71) Some of the olefin metathesis catalysts represented by the structure of Formula (VIII) were obtained as solvates.

(72) In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IVa):

(73) ##STR00011##
wherein:

(74) X.sup.1 and X.sup.2 are independently anionic ligands; generally X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X.sup.1 and X.sup.2 are independently Cl, Br, I or F;

(75) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(76) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2; and

(77) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle.

(78) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IVa), wherein X.sup.1 is Cl; X.sup.2 is Cl; R.sup.1 is morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; R.sup.2 is phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; and R.sup.3 is phenyl or morpholino.

(79) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IX):

(80) ##STR00012##
wherein:

(81) X.sup.1 and X.sup.2 are independently anionic ligands; generally X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X.sup.1 and X.sup.2 are independently Cl, Br, I or F;

(82) X.sup.3 is phenyl or 2-methyl-1-propenyl;

(83) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, unsubstituted unsaturated N-heterocycle, substituted unsaturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2, or —O—(C.sub.1-C.sub.12 alkyl); generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —O—(C.sub.1-C.sub.12 alkyl), or unsubstituted unsaturated N-heterocycle;

(84) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), substituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle; and

(85) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), substituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle.

(86) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IX), wherein X.sup.1 is Cl; X.sup.2 is Cl; X.sup.3 is phenyl; R.sup.1 is morpholino, iso-propoxyl, pyrrolo; R.sup.2 is cyclohexyl, phenyl or morpholino; and R.sup.3 is cyclohexyl, phenyl or morpholino.

(87) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IX), wherein X.sup.1 is Cl; X.sup.2 is Cl; X.sup.3 is 2-methyl-1-propenyl; R.sup.1 is morpholino, iso-propoxyl, pyrrolo; R.sup.2 is cyclohexyl, phenyl or morpholino; and R.sup.3 is cyclohexyl, phenyl or morpholino.

(88) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (X):

(89) ##STR00013##
wherein:

(90) X.sup.1 and X.sup.2 are independently anionic ligands; generally X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X.sup.1 and X.sup.2 are independently Cl, Br, I or F;

(91) X.sup.3 is phenyl or 2-methyl-1-propenyl;

(92) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, unsubstituted unsaturated N-heterocycle, substituted unsaturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl), —N(C.sub.1-C.sub.24 alkyl)C.sub.5-C.sub.24 aryl), —N[(C.sub.1-C.sub.6 alkylene)C.sub.5-C.sub.24 aryl)].sub.2, or —O—(C.sub.1-C.sub.12 alkyl); generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —O—(C.sub.1-C.sub.12 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene(C.sub.6 aryl)].sub.2;

(93) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), substituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1—C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(Ct-C6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(94) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), substituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle;

(95) Y is CR.sup.4 or N; generally Y is N;

(96) R.sup.4 is hydrogen, unsubstituted (C.sub.1-C.sub.12 alkyl), or substituted (C.sub.1-C.sub.12 alkyl);

(97) R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted (C.sub.5-C.sub.24 aryl), or substituted (C.sub.5-C.sub.24 aryl); generally R.sup.5 and R.sup.6 are independently substituted (C.sub.5-C.sub.24 aryl);

(98) Q is a two-atom linkage represented by structures —[CR.sup.7R.sup.8].sub.s—[CR.sup.9R.sup.10].sub.t— or —[CR.sup.11═CR.sup.12]—;

(99) R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are independently hydrogen, unsubstituted (C.sub.1-C.sub.24 alkyl), substituted (C.sub.1-C.sub.24 alkyl), unsubstituted (C.sub.5-C.sub.24 aryl), or substituted (C.sub.1-C.sub.24 aryl); or any two of R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure; generally R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are independently hydrogen, unsubstituted (C.sub.1-C.sub.12 alkyl), substituted (C.sub.1-C.sub.12 alkyl), unsubstituted (C.sub.5-C.sub.14 aryl) or substituted (C.sub.5-C.sub.14 aryl);

(100) R.sup.11 and R.sup.12 are independently hydrogen, unsubstituted (C.sub.1-C.sub.24 alkyl), substituted (C.sub.1-C.sub.24 alkyl), unsubstituted (C.sub.5-C.sub.24 aryl), or substituted (C.sub.5-C.sub.24 aryl); or R.sup.11 and R.sup.12 are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure; and

(101) “s” and “t” are independently 1 or 2; generally “s” and “t” are independently 1.

(102) In one embodiment, the invention provides olefin metathesis catalysts, represented by the structure of Formula (XI),

(103) ##STR00014##
wherein:

(104) X.sup.1 and X.sup.2 are independently anionic ligands; generally X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X.sup.1 and X.sup.2 are independently Cl, Br, I or F;

(105) X.sup.3 is phenyl or 2-methyl-1-propenyl;

(106) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, unsubstituted unsaturated N-heterocycle, substituted unsaturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2, or —O—(C.sub.1-C.sub.12 alkyl); generally R.sup.1 is unsubstituted saturated N-heterocycle, unsubstituted unsaturated N-heterocycle, —O—(C.sub.1-C.sub.12 alkyl);

(107) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), substituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle;

(108) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), substituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.5-C.sub.24 cycloalkyl), unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle; and

(109) R.sup.5 and R.sup.6 are independently unsubstituted (C.sub.5-C.sub.24 aryl), or substituted (C.sub.5-C.sub.24 aryl); generally R.sup.5 and R.sup.6 are independently substituted (C.sub.5-C.sub.24 aryl) with one to three unsubstituted (C.sub.1-C.sub.6 alkyl) groups or substituted (C.sub.1-C.sub.6 alkyl) groups.

(110) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (XI), wherein X.sup.1 is Cl; X.sup.2 is Cl; X.sup.3 is phenyl; R.sup.1 is morpholino, isopropoxy, pyrrolo or piperidino; R.sup.2 is cyclohexyl, morpholino, piperidino or phenyl; R.sup.3 is phenyl, morpholino, piperidino or cyclohexyl; and R.sup.5 and R.sup.6 are independently 2,4,6-trimethyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propylphenyl, or 2-methyl-6-iso-propylphenyl.

(111) In another embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (XI), wherein X.sup.1 is Cl; X.sup.2 is Cl; X.sup.3 is 2-methyl-1-propenyl; R.sup.1 is morpholino, isopropoxy, pyrrolo or piperidino; R.sup.2 is cyclohexyl, morpholino, piperidino or phenyl; R.sup.3 is phenyl, morpholino, piperidino or cyclohexyl; and R.sup.3 and R.sup.6 are independently 2,4,6-trimethyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propylphenyl, or 2-methyl-6-iso-propylphenyl.

(112) Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VI) are found in Table (1):

(113) ##STR00015##

(114) TABLE-US-00001 TABLE 1 Non-limiting examples of olefin metathesis catalysts represented by Formula (VI) Catalyst R.sup.1 R.sup.2 R.sup.3 X.sup.1 X.sup.2 1 Cl Cl 2 0 Cl Cl 3 Cl Cl 4 Cl Cl 5 0 Cl Cl 6 Cl Cl 7 Cl Cl 8 Cl Cl 9 0 Cl Cl 10 Cl Cl 11 Cl Cl 12 0 Cl Cl 13 Cl Cl 14 Cl Cl 15 0 Cl Cl 16 Cl Cl 17 Cl Cl 18 Cl Cl 19 0 Cl Cl 20 Cl Cl 21 Cl Cl

(115) Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VIII) are found in Table (2):

(116) ##STR00079##

(117) TABLE-US-00002 TABLE 2 Non-limiting examples of olefin metathesis catalysts represented by Formula (VIII) Catalyst R.sup.1 R.sup.2 R.sup.3 X.sup.1 X.sup.2 R.sup.5 R.sup.6 22 0 Cl Cl Mes Mes 23 Cl Cl Mes Mes 24 Cl Cl Mes Mes 25 0 Cl Cl Mes Mes 26 Cl Cl Mes Mes 27 Cl Cl Mes Mes 28 00 Cl Cl Mes Mes 29 01 02 03 Cl Cl Mes Mes 30 04 05 06 Cl Cl Mes Mes 31 07 08 09 Cl Cl Mes Mes 32 0 Cl Cl Mes Mes 33 Cl Cl Mes Mes 34 Cl Cl Mes Mes 35 0 Cl Cl Mes Mes 36 Cl Cl Mes Mes 37 Cl Cl Mes Mes 38 0 Cl Cl Mes Mes 39 Cl Cl Mes Mes 40 Cl Cl Mes Mes 41 Cl Cl Mes Mes 42 0 Cl Cl Mes Mes 43 Cl Cl DIPP DIPP 44 Cl Cl DIPP DIPP 45 0 Cl Cl DIPP DIPP 46 Cl Cl DIPP DIPP 47 Cl Cl DIPP DIPP 48 0 Cl Cl DIPP DIPP 49 Cl Cl DIPP DIPP 50 Cl Cl DIPP DIPP 51 Cl Cl DIPP DIPP 52 0 Cl Cl DIPP DIPP 53 Cl Cl DIPP DIPP 54 Cl Cl DIPP DIPP 55 0 Cl Cl DIPP DIPP 56 Cl Cl DIPP DIPP 57 Cl Cl DIPP DIPP 58 0 Cl Cl DIPP DIPP 59 Cl Cl DIPP DIPP 60 Cl Cl DIPP DIPP 61 Cl Cl DIPP DIPP 62 00 01 02 Cl Cl DIPP DIPP 63 03 04 05 Cl Cl DIPP DIPP 64 06 07 08 Cl Cl MIPP MIPP 65 09 0 Cl Cl MIPP MIPP 66 Cl Cl MIPP MIPP 67 Cl Cl MIPP MIPP 68 0 Cl Cl MIPP MIPP 69 Cl Cl MIPP MIPP 70 Cl Cl MIPP MIPP 71 Cl Cl MIPP MIPP 72 0 Cl Cl MIPP MIPP 73 Cl Cl MIPP MIPP 74 Cl Cl MIPP MIPP 75 0 Cl Cl MIPP MIPP 76 Cl Cl MIPP MIPP 77 Cl Cl MIPP MIPP 78 0 Cl Cl MIPP MIPP 79 Cl Cl MIPP MIPP 80 Cl Cl MIPP MIPP 81 Cl Cl MIPP MIPP 82 0 Cl Cl MIPP MIPP 83 Cl Cl MIPP MIPP 84 Cl Cl MIPP MIPP wherein: Mes is MIPP is 0and DIPP is

(118) Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (IVa) are found in Table (3):

(119) ##STR00272##

(120) TABLE-US-00003 TABLE 3 Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (IVa) Catalyst R.sup.1 R.sup.2 R.sup.3 X.sup.1 X.sup.2 85 Cl Cl 86 Cl Cl 87 0 Cl Cl 88 Cl Cl 89 Cl Cl 90 0 Cl Cl 91 Cl Cl 92 Cl Cl 93 Cl Cl 94 00 01 02 Cl Cl 95 03 04 05 Cl Cl 96 06 07 08 Cl Cl 97 09 0 Cl Cl 98 Cl Cl 99 Cl Cl 100 0 Cl Cl 101 Cl Cl 102 Cl Cl 103 Cl Cl 104 0 Cl Cl 105 Cl Cl

(121) Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (IX) are found in Table (4):

(122) ##STR00336##

Table (4)

(123) Non-limiting examples of olefin metathesis catalysts represented by the structure of

(124) TABLE-US-00004 Formula IX Catalyst R.sup.1 R.sup.2 R.sup.3 X.sup.1 X.sup.2 X.sup.3 106 Cl Cl 0 107 Cl Cl 108 Cl Cl 109 0 Cl Cl 110 Cl Cl 111 Cl Cl 0 112 Cl Cl 113 Cl Cl 114 0 Cl Cl 115 Cl Cl 116 Cl Cl 0 117 Cl Cl 118 Cl Cl 119 0 Cl Cl

(125) Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (XI) are found in Table (5):

(126) ##STR00393##

Table (5)

(127) Non-limiting examples of olefin metathesis catalysts represented b the structure of

(128) TABLE-US-00005 Formula (XI) Catalyst R.sup.1 R.sup.2 R.sup.3 X.sup.1 X.sup.2 X.sup.3 R.sup.5 R.sup.6 120 Cl Cl Mes Mes 121 00 Cl Cl 01 Mes Mes 122 02 03 04 Cl Cl 05 Mes Mes 123 06 07 08 Cl Cl 09 Mes Mes 124 0 Cl Cl Mes Mes 125 Cl Cl Mes Mes 126 0 Cl Cl Mes Mes 127 Cl Cl Mes Mes 128 Cl Cl Mes Mes 129 0 Cl Cl Mes Mes 130 Cl Cl Mes Mes 131 0 Cl Cl Mes Mes 132 Cl Cl Mes Mes 133 Cl Cl Mes Mes 134 0 Cl Cl Mes Mes 135 Cl Cl Mes Mes 136 0 Cl Cl Mes Mes 137 Cl Cl Mes Mes 138 Cl Cl Mes Mes 139 0 Cl Cl Mes Mes 140 Cl Cl DIPP DIPP 141 0 Cl Cl DIPP DIPP 142 Cl Cl DIPP DIPP 143 Cl Cl DIPP DIPP 144 0 Cl Cl DIPP DIPP 145 Cl Cl DIPP DIPP 146 00 Cl Cl 01 DIPP DIPP 147 02 03 04 Cl Cl 05 DIPP DIPP 148 06 07 08 Cl Cl 09 DIPP DIPP 149 0 Cl Cl DIPP DIPP 150 Cl Cl DIPP DIPP 151 0 Cl Cl DIPP DIPP 152 Cl Cl DIPP DIPP 153 Cl Cl DIPP DIPP 154 0 Cl Cl DIPP DIPP 155 Cl Cl DIPP DIPP 156 0 Cl Cl DIPP DIPP 157 Cl Cl DIPP DIPP 158 Cl Cl DIPP DIPP 158 0 Cl Cl DIPP DIPP 159 Cl Cl MIPP MIPP 160 0 Cl Cl MIPP MIPP 161 Cl Cl MIPP MIPP 162 Cl Cl MIPP MIPP 163 0 Cl Cl MIPP MIPP 164 Cl Cl MIPP MIPP 165 0 Cl Cl MIPP MIPP 166 Cl Cl MIPP MIPP 167 Cl Cl MIPP MIPP 168 0 Cl Cl MIPP MIPP 169 Cl Cl MIPP MIPP 170 00 Cl Cl 01 MIPP MIPP 171 02 03 04 Cl Cl 05 MIPP MIPP 172 06 07 08 Cl Cl 09 MIPP MIPP 173 0 Cl Cl MIPP MIPP 174 Cl Cl MIPP MIPP 175 0 Cl Cl MIPP MIPP 176 Cl Cl MIPP MIPP 177 Cl Cl MIPP MIPP 178 0 Cl Cl MIPP MIPP wherein:

(129) The present invention concerns also processes for preparing the olefin metathesis catalysts described above. The olefin metathesis catalysts according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry.

(130) Synthetic Scheme 1 illustrates how the olefin metathesis catalysts of Formula (VI), Formula (VII), and Formula (VIII) can be synthesized.

(131) ##STR00637##

(132) Synthetic Scheme 2 illustrates how olefin metathesis catalysts of Formula (IVa) can be synthesized.

(133) ##STR00638##

(134) Synthetic Scheme 3 illustrates how the olefin metathesis catalysts of Formula (IX), Formula (X), and Formula (XI) can be synthesized.

(135) ##STR00639##

(136) In synthetic Schemes 1, 2, and 3, substituents X.sup.1, X.sup.2, X.sup.3, R.sup.1, R.sup.2, R.sup.3, Q, Y, R.sup.5, and R are as defined herein.

(137) Generally, the reactions take place under degassed N.sub.2 at room temperature or at high temperature in an inert solvent (toluene, THF, MeTHF, dioxane and the like). Once the reaction is completed, the mixture is cooled to room temperature, the solvent is removed under high vacuum, and the residue is purified on a silica gel column and then recrystallized to afford the new olefin metathesis catalysts.

(138) In another embodiment, the invention concerns methods of using the olefin metathesis catalysts of the invention, in the synthesis of related olefin metathesis catalysts. The ruthenium olefin metathesis catalysts of the invention are excellent precursors for various Second Generation Grubbs ruthenium olefin metathesis catalysts. The Second Generation Grubbs ruthenium olefin metathesis catalysts synthesized during these procedures are obtained in higher yield and with higher purity, which presents an advantage compared to the existing synthetic procedures.

(139) The invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (A) starting with an olefin metathesis catalyst of Formula (VIII).

(140) ##STR00640##

(141) In a typical procedure, as shown in Scheme 4, the PR.sup.1R.sup.2R.sup.3 ligand of the olefin metathesis catalyst represented by Formula (VIII) can be exchanged with a PR.sup.dR.sup.eOR.sup.f ligand at room temperature in an inert solvent, such as dichloromethane or toluene, wherein:

(142) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(143) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(144) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle;

(145) R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted C.sub.5-C.sub.24 aryl, or substituted C.sub.5-C.sub.24 aryl; generally R.sup.5 and R.sup.6 are independently substituted C.sub.5-C.sub.24 aryl with one to three unsubstituted (C.sub.1-C.sub.6 alkyl) groups or substituted (C.sub.1-C.sub.6 alkyl) groups; typically, R.sup.5 and R.sup.6 are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl;

(146) X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally X.sup.1 and X.sup.2 are independently Cl, Br, I or F; typically X.sup.1 and X.sup.2 are independently Cl;

(147) R.sup.d is unsubstituted C.sub.1-C.sub.10 alkyl, substituted C.sub.1-C.sub.10 alkyl, substituted C.sub.6-C.sub.10 aryl, unsubstituted C.sub.6-C.sub.10 aryl, substituted C.sub.3-C.sub.8 cycloalkyl or unsubstituted C.sub.3-C.sub.8 cycloalkyl; generally R.sup.d is unsubstituted C.sub.1-C.sub.10 alkyl or unsubstituted C.sub.6-C.sub.10 aryl; typically R.sup.d is phenyl;

(148) R.sup.e is unsubstituted C.sub.1-C.sub.10 alkyl, substituted C.sub.1-C.sub.10 alkyl, substituted C.sub.6-C.sub.10 aryl, unsubstituted C.sub.6-C.sub.10 aryl, substituted C.sub.3-C.sub.8 cycloalkyl or unsubstituted C.sub.3-C.sub.8 cycloalkyl; generally R.sup.e is unsubstituted C.sub.1-C.sub.10 alkyl or unsubstituted C.sub.6-C.sub.10 aryl; typically R.sup.e is phenyl; and

(149) R.sup.f is unsubstituted C.sub.1-C.sub.10 alkyl, substituted C.sub.1-C.sub.10 alkyl, substituted C.sub.6-C.sub.10 aryl, unsubstituted C.sub.6-C.sub.10 aryl, substituted C.sub.3-C.sub.8 cycloalkyl or unsubstituted C.sub.3-C.sub.8 cycloalkyl; generally R.sup.f is unsubstituted C.sub.1-C.sub.10 alkyl, unsubstituted C.sub.6-C.sub.10 aryl or unsubstituted C.sub.6-C.sub.10 aryl; typically, R.sup.f is phenyl, methyl, p-(OMe)phenyl, iso-propyl or ethyl.

(150) The invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (B) starting with an olefin metathesis catalyst of Formula (VIII).

(151) ##STR00641##

(152) In a typical procedure, as shown in Scheme 5, the PR.sup.1R.sup.2R.sup.3 ligand of the olefin metathesis catalyst represented by Formula (VIII) can be exchanged with a PR.sup.gOR.sup.hOR.sup.i ligand or a PR.sup.gR.sup.hOR.sup.i ligand at room temperature in an inert solvent, such as dichloromethane or toluene, wherein:

(153) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(154) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(155) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle;

(156) R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted C.sub.5-C.sub.24 aryl, or substituted C.sub.5-C.sub.24 aryl; generally R.sup.5 and R.sup.6 are independently substituted C.sub.5-C.sub.24 aryl with one to three unsubstituted (C.sub.1-C.sub.6 alkyl) groups or substituted (C.sub.1-C.sub.6 alkyl) groups; typically, R.sup.5 and R.sup.6 are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl;

(157) X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally X.sup.1 and X.sup.2 are independently Cl, Br, I or F; typically X.sup.1 and X.sup.2 are independently Cl;

(158) R.sup.g is unsubstituted C.sub.1-C.sub.10 alkyl, substituted C.sub.1-C.sub.10 alkyl, substituted C.sub.6-C.sub.10 aryl, unsubstituted C.sub.6-C.sub.10 aryl, substituted C.sub.3-C.sub.8 cycloalkyl or unsubstituted C.sub.3-C.sub.8 cycloalkyl; generally R.sup.g is unsubstituted C.sub.1-C.sub.10 alkyl or unsubstituted C.sub.6-C.sub.10 aryl; typically R.sup.g is phenyl;

(159) R.sup.h is unsubstituted C.sub.1-C.sub.10 alkyl, substituted C.sub.1-C.sub.10 alkyl, substituted C.sub.6-C.sub.10 aryl, unsubstituted C.sub.6-C.sub.10 aryl, substituted C.sub.3-C.sub.8 cycloalkyl or unsubstituted C.sub.3-C.sub.8 cycloalkyl; generally R.sup.h is unsubstituted C.sub.1-C.sub.10 alkyl or unsubstituted C.sub.6-C.sub.10 aryl; typically R.sup.h is phenyl or methyl; and

(160) R.sup.i is unsubstituted C.sub.1-C.sub.10 alkyl, substituted C.sub.1-C.sub.10 alkyl, substituted C.sub.6-C.sub.10 aryl, unsubstituted C.sub.6-C.sub.10 aryl, substituted C.sub.3-C.sub.8 cycloalkyl or unsubstituted C.sub.3-C.sub.8 cycloalkyl; generally R.sup.i is unsubstituted C.sub.1-C.sub.10 alkyl or unsubstituted C.sub.6-C.sub.10 aryl; typically R.sup.i is phenyl or methyl.

(161) In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (C) starting with an olefin metathesis catalyst of Formula (IVa).

(162) ##STR00642##

(163) In a typical procedure, as shown in Scheme 6, the PR.sup.1R.sup.2R.sup.3 ligand of the olefin metathesis catalyst represented by Formula (IVa) can be exchanged with a NHC ligand,

(164) ##STR00643##
wherein:

(165) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(166) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(167) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle;

(168) R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted C.sub.5-C.sub.24 aryl, or substituted C.sub.5-C.sub.24 aryl; generally R.sup.5 and R.sup.6 are independently substituted C.sub.5-C.sub.24 aryl with one to three unsubstituted (C.sub.1-C.sub.6 alkyl) groups or substituted (C.sub.1-C.sub.6 alkyl) groups; typically, R.sup.5 and R.sup.6 are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl; and

(169) X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally X.sup.1 and X.sup.2 are independently Cl, Br, I or F; typically X.sup.1 and X.sup.2 are independently Cl.

(170) In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (C) starting with an olefin metathesis catalyst of Formula (VIII).

(171) ##STR00644##

(172) In a typical procedure, as shown in Scheme 7, the —PR.sup.1R.sup.2R.sup.3 ligand of the olefin metathesis catalyst represented by Formula (VIII) can be exchanged with a Grubbs-Hoveyda ligand, wherein:

(173) R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.1 is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(174) R.sup.2 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C.sub.1-C.sub.24 alkyl), —N(C.sub.1-C.sub.24 alkyl).sub.2, —NH(C.sub.5-C.sub.24 aryl), —N(C.sub.5-C.sub.24 aryl).sub.2, —N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl) or —N[(C.sub.1-C.sub.6 alkylene)(C.sub.5-C.sub.24 aryl)].sub.2; generally R.sup.2 is unsubstituted (C.sub.6 aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —N(C.sub.1-C.sub.6 alkyl).sub.2, —N(C.sub.1-C.sub.6 alkyl)(C.sub.6 aryl) or —N[(C.sub.1-C.sub.3 alkylene)(C.sub.6 aryl)].sub.2;

(175) R.sup.3 is unsubstituted (C.sub.5-C.sub.24 aryl), substituted (C.sub.5-C.sub.24 aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; generally R.sup.3 is unsubstituted (C.sub.6 aryl) or unsubstituted saturated N-heterocycle;

(176) R.sup.5 and R.sup.6 are independently hydrogen, unsubstituted C.sub.5-C.sub.24 aryl, or substituted C.sub.5-C.sub.24 aryl; generally R.sup.5 and R.sup.6 are independently substituted C.sub.5-C.sub.24 aryl with one to three unsubstituted (C.sub.1-C.sub.6 alkyl) groups or substituted (C.sub.1-C.sub.6 alkyl) groups; typically, R.sup.5 and R.sup.6 are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl;

(177) X.sup.1 and X.sup.2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally X.sup.1 and X.sup.2 are independently Cl, Br, I or F; typically X.sup.1 and X.sup.2 are independently Cl.

(178) R.sup.k is hydrogen, halogen, —NO.sub.2, —CN, —CF.sub.3, —SO.sub.2NR.sup.s.sub.2, —NHC(O)CF.sub.3, —NHC(O)C.sub.6F.sub.5, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R.sup.k is hydrogen;

(179) R.sup.l is hydrogen, halogen, —NO.sub.2, —CN, —CF.sub.3, —SO.sub.2NR.sup.s.sub.2, —NHC(O)CF.sub.3, —NHC(O)C.sub.6F.sub.5, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R.sup.l is hydrogen;

(180) R.sup.m is hydrogen, halogen, —NO.sub.2, —CN, —CF.sub.3, —SO.sub.2NR.sup.s.sub.2, —NHC(O)CF.sub.3, —NHC(O)C.sub.6F.sub.5, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R.sup.m is hydrogen, —NO.sub.2, —CN, —CF.sub.3, —SO.sub.2NR.sup.s.sub.2, —NHC(O)CF.sub.3, —NHC(O)C.sub.6F.sub.5, or —NHC(O)OtBu; specifically R.sup.m is hydrogen;

(181) R.sup.n is hydrogen, halogen, —NO.sub.2, —CN, —CF.sub.3, —SO.sub.2NR.sup.s.sub.2, —NHC(O)CF.sub.3, —NHC(O)C.sub.6F.sub.5, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R.sup.n is hydrogen; and

(182) R.sup.s is hydrogen or C.sub.1-C.sub.6 alkyl; typically R.sup.s is hydrogen, methyl, ethyl or n-propyl; and

(183) R.sup.q is unsubstituted hydrocarbyl, substituted hydrocarbyl; generally, R.sup.q is C.sub.1-C.sub.10 alkyl; typically, R.sup.q is iso-propyl.

(184) At this stage, those skilled in the art will appreciate that many additional compounds that fall under the scope of the invention can be prepared by performing various common chemical reactions. Details of certain specific chemical transformations are provided in the examples.

(185) For example, the olefin metathesis catalysts are typically added to a resin composition as a solid, a solution, or as a suspension. When the olefin metathesis catalysts are added to a resin composition as a suspension, the olefin metathesis catalysts are suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-iso-propylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst(s), and which is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boiling impurity in the olefin metathesis reaction.

Olefins

(186) Resin compositions that may be used with the present invention disclosed herein comprise one or more cyclic olefins. Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or poly-unsaturated C.sub.5 to C.sub.24 hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition.

(187) Examples of bicyclic and polycyclic olefins thus include, without limitation, dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; C.sub.2-C.sub.12 hydrocarbyl substituted norbornenes; 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; 5-butenyl-2-norbornene; 5-tolyl-norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene; bicyclo[2.2.1]hept-2-ene-2-carboxylic acid, 2-ethylhexyl ester; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxy carbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyl tetracyclododecene; 8-ethyltetracyclododecene; 8-methoxy carbonyltetracyclo dodecene; 8-methyl-8-tetra cyclododecene; 8-cyanotetracyclo dodecene; pentacyclopentadecene; pentacyclo hexadecene; bicyclo[2.2.1]hept-2-ene-5-phenoxymethyl; 2-ethylhexyl ester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; 2-hydroxyethyl ester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; bicyclo[2.2.1]hept-5-ene-2-methanol; bicyclo[2.2.1]hept-5-ene-2-heptanoic acid-methyl ester; bicyclo[2.2.1]hept-5-ene-2-hexanoic acid-methyl ester; 1,4:5,8-dimethanonaphthalene, 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro; bicyclo[2.2.1]hept-5-ene-2-octanoic acid-methyl ester; 1,4:5,8-dimethano naphthalene; 2-butyl-1,2,3,4,4a,5,8,8a-octahydro; ethylidenetetracyclododecene; 2-vinyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethano naphthalene; and the like, and their structural isomers, stereoisomers, and mixtures thereof.

EXPERIMENTAL

General Information—Materials and Methods

(188) In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. The examples are to be considered as not being limiting of the invention described herein.

(189) All reactions involving metal complexes were conducted in oven-dried glassware under an argon or nitrogen atmosphere using standard Schlenk techniques. Chemicals and solvents were obtained from Sigma-Aldrich, Strem, Alfa Aesar, Nexeo, Brenntag, AG Layne and TCI. Commercially available reagents were used as received unless otherwise noted. Silica gel was purchased from Fisher (0.040-0.063 μm, EMD Millipore). Solvents were dried by passing through an activated alumina column (n-pentane, benzene, toluene, Et20, and THF).

(190) SIMes.HBr, SIMes.HCl, SIPr.HCl, P426, P510, 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene and Catalysts C959, C931, C848, C831, C949, C601, C727, C787, and C765 were prepared using known methods.

(191) The crystallographic measurements were performed at 100(2) K using a Bruker APEX-II CCD area detector diffractometer (Mo-K.sub.α radiation, λ=0.71073 Å). In each case, a specimen of suitable size and quality was selected and mounted onto a nylon loop. The structures were solved by direct methods, which successfully located most of the nonhydrogen atoms. Semi-empirical absorption corrections were applied. Subsequent refinement on F.sup.2 using the SHELXTL/PC package (version 6.1) allowed location of the remaining non-hydrogen atoms. Depending on the experimental conditions, some of the olefin metathesis catalysts of the invention were obtained as solvates.

(192) Ultrene® 99 dicyclopentadiene (DCPD) was obtained from Cymetech Corporation. A modified DCPD base resin containing 20-25% tricyclopentadiene (and small amounts of higher cyclopentadiene homologs) (DCPD-HT) was prepared by heat treatment of Ultrene® 99 DCPD generally as described in U.S. Pat. No. 4,899,005.

(193) .sup.1H and .sup.13C NMR spectra were recorded on a Varian 400 MHz spectrometer. Chemical shifts are reported in ppm downfield from Me4Si by using the residual solvent peak as an internal standard (CDCl.sub.3 —δ 7.24 ppm; CD.sub.2Cl.sub.2—δ 5.32 ppm). .sup.31P NMR used an external standard of 85% H.sub.3PO.sub.4, referenced to 0 ppm. Spectra were analyzed and processed using MestReNova software. Deuterated solvents were purchased from Cambridge Isotopes Laboratories, Inc. and were degassed and stored over activated 3 Å molecular sieves prior to use.

(194) The following abbreviations are used in the examples: mL milliliter L liter ° C. degrees Celsius CD.sub.2Cl.sub.2 deuterated dichloromethane CDCl.sub.3 deuterated chloroform C.sub.6D.sub.6 deuterated benzene SIMes.HBr N,N′-bis-(2,4,6-trimethylphenylamino)ethane dihydrobromide SIMes.HCl N,N′-bis-(2,4,6-trimethylphenylamino)ethane dihydrochloride SIPr.HCl 1,3-bis(2,6-di-iso-propylphenyl)-4,5-dihydroimidazolium chloride Ar argon HCl hydrochloric acid KHMDS potassium bis(trimethylsilyl)amide r.t. room temperature

(195) ##STR00645## C765 Dichloro(3-methyl-2-butenylidene)bis(triphenylphosphine) ruthenium [CAS 191609-95-7]

(196) ##STR00646## C727 [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)bis(pyridine)-Ruthenium [CAS 357186-58-4]

(197) ##STR00647## 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene C959 (PPh.sub.3).sub.3Ru(Cl).sub.2tris(triphenylphosphine)ruthenium(II) dichloride [CAS 15529-49-4] (2-Me)THF 2-methyltetrahydrofuran THF tetrahydrofuran

(198) ##STR00648## C787 Benzylidenedichlorobis(triphenylphosphine)ruthenium [CAS 172222-26-3]

(199) ##STR00649## C848 Dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine) ruthenium (II) [CAS 246047-72-3]

(200) ##STR00650## C831 Dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(triphenylphosphine) ruthenium (II) [CAS 357261-84-8] PTSA p-Toluenesulfonic acid

(201) ##STR00651## C931 [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro (phenylindenylidene)(triphenylphosphine)ruthenium(II) [CAS 340810-50-6]

(202) ##STR00652## C949 [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro (phenylindenylidene) (tricyclohexylphosphine) ruthenium(II) [CAS 536724-67-1]

(203) ##STR00653## C601 Dichloro(2-isopropoxyphenylmethylene) (tricyclohexylphosphine)ruthenium (II) [CAS 203714-71-0]

(204) ##STR00654## P426 1,3-Bis(2,4,6-trimethylphenyl)-2-(trichloromethyl)imidazolidine [CAS 260054-47-5]

(205) ##STR00655## P510 1,3-bis[2,6-bis(1-methylethyl)phenyl]-2-(trichloromethyl) imidazolidine [CAS 465543-05-9]

EXAMPLES

Example 1

Synthesis of C973

(206) ##STR00656##

(207) In a 3 L, 3-neck round bottom flask were added C959 (100.0 g, 104.2 mmol), 1,1-diphenyl-2-propyn-1-ol (24.9 g, 119.8 mmol), and triphenylphosphine (27.3 g, 104.2 mmol)under air. The flask was equipped with a thermocouple and rubber suba-seal septum and then it was placed under Ar using Schlenk technique. The reagents and products of this reaction are highly air sensitive in solution. A 1 L addition funnel was attached to the flask under a flow of Ar. To the addition funnel were added (2-Me)THF (1 L) and 4 M HCl (25.6 mL, 104.2 mmol) in dioxane using Schlenk technique. The solution was added over 10 minutes at room temperature with stirring. Another 0.75 L (2-Me)THF were added directly to the flask. The addition funnel was replaced with a glass stopper under a flow of Ar and the flask was lowered into a pre-heated oil bath at 65° C. The reaction was monitored by .sup.31P NMR. When conversion was deemed to be complete, the reaction flask was removed from the oil bath and hot filtered via cannula transfer through a celite pad (in an evacuated Schlenk filter) into a Schlenk flask. Approximately 85% (2-Me)THF was removed at room temperature (water bath) under vacuum. The resulting slurry was cooled to 0° C. then filtered on a coarse glass frit under air. The solid was washed quickly with 3×50 mL portions of 0° C. (2-Me)THF followed by hexanes (200 mL) (r.t.) and 2-propanol (100 mL). The solid from the frit was re-slurred with hexanes (200 mL) and filtered again. The solid was air-dried until no condensation was seen on the outside of the glass frit, then transferred to a 200 mL round bottom flask and dried under high vacuum overnight. The final .sup.1H NMR and .sup.31P NMR in CDCl.sub.3 indicate that the complex is a 1:1 adduct of (PPh.sub.3).sub.2Ru(PhInd)Cl.sub.2, and (2-Me)THF, C973, for a final molecular weight of 973 g/mol. Yield=74.1 g (73%).

(208) .sup.1H NMR (400 MHz in CDCl.sub.3 at r.t.): δ=7.2-7.6 (overlapping CDCl.sub.3 and aromatics), 7.07 (d, Ind, 1H), 6.62 (t, Ind, 1H), 6.43 (s, Ind, 1H), 3.92 (m, (2-Me)THF, 2H), 3.70 (m, (2-Me)THF, 1H), 1.88-1.98 (overlapping m, (2-Me)THF, 3H), 1.41 (m, (2-Me)THF, 1H), 1.23 (d, (2-Me)THF, 3H).

Example 2

Synthesis of C905

(209) ##STR00657##

(210) To a 40 mL scintillation vial equipped with a magnetic stir bar were added C973 (0.750 mg, 0.771 mmol), Ph.sub.2P[N(C.sub.2H.sub.4).sub.2O] ([CAS 13743-27-6] 0.837 g, 3.08 mmol), and diethyl ether (20 mL). The suspension was allowed to stir for 14 hours at ambient temperature. The resulting precipitate was isolated by filtration, washed with diethyl ether (5 mL) followed by diethyl ether/hexanes (1:1, 10 mL), then dried in vacuum to afford C905 as a red/brown powder (0.507 g, 72.7% yield).

(211) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.71 (m, 6H), 7.61-7.50 (m, 4H), 7.48-7.40 (m, 5H), 7.40-7.31 (m, 11H), 7.24 (d, J=7.4 Hz, 2H), 6.79 (t, J=7.4 Hz, 1H), 6.38 (s, 1H), 3.42 (br s, 8H), 2.81 (br s, 8H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 79.3 (s).

Example 3

Synthesis of C940

(212) ##STR00658##

(213) To a 40 mL scintillation vial equipped with a magnetic stir bar were added C905 (0.200 mg, 0.221 mmol), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (0.071 g, 0.23 mmol), and toluene (10 mL). The resulting solution was stirred for 2 hours, devolatilized, and the resulting residue recrystallized from toluene/pentane at −35° C. The resulting brown crystals were separated by filtration and dried in vacuum affording C940 (0.146 g, 70.1% yield). FIG. 1 shows the ORTEP diagram of C940.

(214) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.78 (d, J=7.6 Hz, 1H), 7.56-7.33 (m, 7H), 7.27 (t, J=7.3 Hz, 1H), 7.24-7.11 (m, 6H), 7.08-7.01 (m, 2H), 6.98 (d, J=6.5 Hz, 3H), 6.93 (t, J=7.6 Hz, 1H), 6.54 (s, 1H), 6.39 (s, 1H), 6.00 (s, 1H), 4.07-3.97 (m, 2H), 3.90-3.71 (m, 2H), 3.37-3.22 (m, 4H), 2.65 (s, 6H), 2.62-2.48 (m, 4H), 2.38 (s, 3H), 2.12 (s, 3H), 1.97 (s, 3H), 1.81 (s, 3H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 76.3 (s).

Example 4

Synthesis of C923

(215) ##STR00659##

(216) To a 20 mL scintillation vial equipped with a magnetic stir bar were added C973 (0.500 mg, 0.514 mmol), 4,4′-(phenylphosphinidene)bismorpholine ([CAS 13337-35-4] 0.576 g, 2.06 mmol), and diethyl ether (10 mL). The suspension was allowed to stir for 14 hours at ambient temperature. The resulting precipitate was isolated by filtration, washed with diethyl ether (5 mL) followed by diethyl ether/hexanes (1:1, 10 mL) and hexanes (10 mL), then dried in vacuum to afford C923 as a red/brown powder (0.313 g, 66.0% yield).

(217) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.95-7.15 (m, 18H), 7.15-6.30 (m, 2H), 3.49 (br s, 16H), 3.02 (br s, 16H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 97.3 (br s).

Example 5

Synthesis of C949

(218) ##STR00660##

(219) To a 20 mL scintillation vial equipped with a magnetic stir bar were added SIMes.HBr (0.110 mg, 0.285 mmol), KHMDS (0.057 g, 0.285 mmol), and toluene (2 mL). The resulting reaction was allowed to stir for 30 minutes at ambient temperature, then it was filtered through a pad of celite, and combined with C923 and hexanes (8 mL) in a 20 mL scintillation vial equipped with a magnetic stir bar. The resulting suspension was subsequently stirred for 6 hours at ambient temperature. The resulting precipitate was isolated by filtration, washed with toluene/hexanes (3:7, 2×10 mL) followed by hexanes (10 mL) then dried in vacuum, to afford C949 as a red/brown powder (0.239 g, 93.0% yield).

(220) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.91 (d, J=7.3 Hz, 1H), 7.66 (d, J=7.6 Hz, 2H), 7.56 (t, J=6.9 Hz, 1H), 7.42 (t, J=7.6 Hz, 2H), 7.25 (t, J=7.3 Hz, 1H), 7.21-7.07 (m, 3H), 7.09-6.93 (m, 6H), 6.54 (s, 1H), 6.38 (s, 1H), 5.96 (s, 1H), 4.10-3.97 (m, 2H), 3.90-3.70 (m, 2H), 3.29 (br s, 4H), 3.26-3.03 (m, 4H), 2.96-2.80 (m, 4H), 2.78-2.69 (m, 4H), 2.67 (s, 3H), 2.66 (s, 3H), 2.38 (s, 3H), 2.13 (s, 3H), 1.97 (s, 3H), 1.76 (s, 3H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 97.4 (s).

Example 6

Synthesis of C941

(221) ##STR00661##

(222) To a 40 mL scintillation vial equipped with a magnetic stir bar were added C973 (1.00 g, 1.03 mmol), 4,4″,4′″-phosphinidyltrismorpholine ([CAS 5815-61-2] 1.19 g, 4.11 mmol), and diethyl ether (30 mL). The suspension was allowed to stir for 14 hours at ambient temperature. The resulting precipitate was isolated by filtration, washed with diethyl ether (4×15 mL) followed by hexanes (2×10 mL), then dried in vacuum to afford C941 as a red powder (0.740 g, 76.5% yield).

(223) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 8.61-8.44 (m, 1H), 7.87-7.72 (m, 2H), 7.60 (t, J=7.0 Hz, 1H), 7.45 (t, J=7.4 Hz, 3H), 7.40-7.20 (m, 3H), 3.52 (s, 24H), 3.15 (s, 24H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 100.1 (br s).

Example 7

Synthesis of C958

(224) ##STR00662##

(225) To a 20 mL scintillation vial equipped with a magnetic stir bar was added C941 (0.500 g, 0.531 mmol), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (0.171 g, 0.558 mmol), and diethyl ether (10 mL). The resulting suspension was allowed to stir for 8 hours at ambient temperature. The resulting precipitate was isolated by filtration, washed with diethyl ether (2×10 mL) followed by hexanes (10 mL) then dried in vacuum to afford C958 as a red/brown powder (0.434 g, 85.3% yield). FIG. 2 shows the ORTEP diagram of C958.

(226) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 8.41 (d, J=7.4 Hz, 1H), 7.70 (d, J=7.8 Hz, 2H), 7.54 (t, J=7.4 Hz, 1H), 7.43 (t, J=7.5 Hz, 2H), 7.30-7.20 (m, 2H), 7.14 (t, J=7.5 Hz, 2H), 7.09-6.98 (m, 3H), 6.42 (s, 1H), 5.99 (s, 1H), 4.07-3.97 (m, 2H), 3.91-3.72 (m, 2H), 3.23 (s, 12H), 2.79 (s, 12H), 2.71 (s, 3H), 2.67 (s, 3H), 2.36 (s, 3H), 2.17 (s, 3H), 2.10 (s, 3H), 1.81 (s, 3H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 108.8 (s).

Example 8

Synthesis of C1042

(227) ##STR00663##

(228) To a 20 mL scintillation vial equipped with a magnetic stir bar was added 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolium chloride (0.238 g, 0.558 mmol), potassium bis(trimethylsilyl)amide (0.111 g, 0.558 mmol), and toluene (5 mL). The resulting reaction was allowed to stir for 30 minutes at ambient temperature, filtered through a pad of celite, and combined with C941 (0.500 g, 0.531 mmol) and heptanes (15 mL) in a 40 mL scintillation vial equipped with a magnetic stir bar. The resulting suspension was subsequently stirred for 3 hours at ambient temperature. The resulting precipitate was isolated by filtration, washed with toluene/heptanes (1:4, 2×10 mL) followed by heptanes (10 mL) then dried in vacuum to afford C1042 (0.436 g, 78.7% yield) as a red/brown powder.

(229) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.66 (d, J=7.4 Hz, 1H), 7.64 (d, J=8.3 Hz, 2H), 7.53-7.42 (m, 2H), 7.37 (t, J=6.5 Hz, 4H), 7.23 (t, J=7.5 Hz, 1H), 7.12 (t, J=7.5 Hz, 1H), 7.04 (d, J=7.2 Hz, 1H), 6.94 (s, 1H), 6.73-6.67 (m, 2H), 6.61-6.56 (m, 1H), 4.27-4.18 (m, 1H), 4.17-3.91 (m, 4H), 3.91-3.81 (m, 1H), 3.59-3.49 (m, 1H), 3.31-3.18 (m, 12H), 3.19-3.10 (m, 1H), 2.93-2.77 (m, 6H), 2.75-2.63 (m, 6H), 1.58 (d, J=6.4 Hz, 3H), 1.53 (d, J=6.4 Hz, 3H), 1.37 (d, J=6.6 Hz, 3H), 1.26 (d, J=6.8 Hz, 3H), 1.22 (d, J=6.8 Hz, 3H), 1.09 (d, J=6.8 Hz, 3H), 0.94 (d, J=6.8 Hz, 3H), 0.82 (d, J=6.6 Hz, 3H). .sup.31P NMR (162 MHz, CDCl.sub.3) δ 102.8 (s).

Example 9

Synthesis of C1050

(230) ##STR00664##

(231) To a 20 mL scintillation vial equipped with a magnetic stir bar were added SIMes.HBr (0.173 mg, 0.446 mmol), KHMDS (0.089 g, 0.446 mmol), and toluene (4 mL). The resulting reaction was allowed to stir for 30 minutes at ambient temperature, then filtered through a pad of celite, and combined with C941 (0.400 g, 0.425 mmol) and hexanes (16 mL) in a 40 mL scintillation vial equipped with a magnetic stir bar. The resulting suspension was subsequently stirred for 4 hours at ambient temperature. The resulting precipitate was isolated by filtration, washed with toluene/hexanes (1:5, 2×10 mL) followed by hexanes (10 mL) then dried in vacuum to afford C1050 as a red/brown powder (0.406 g, 91.0% yield).

(232) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 8.41 (d, J=7.5 Hz, 1H), 7.70 (d, J=7.8 Hz, 2H), 7.54 (t, J=7.2 Hz, 1H), 7.43 (t, J=7.6 Hz, 2H), 7.30-7.20 (m, 4H), 7.20-7.10 (m, 4H), 7.09-6.98 (m, 3H), 6.42 (s, 1H), 5.99 (s, 1H), 4.07-3.97 (m, 2H), 3.91-3.72 (m, 2H), 3.24 (s, 12H), 2.79 (s, 12H), 2.71 (s, 3H), 2.67 (s, 3H), 2.36 (s, 3H), 2.34 (s, 3H), 2.17 (s, 3H), 2.10 (s, 3H), 1.81 (s, 3H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 108.9 (s).

Example 10

Synthesis of C947

(233) ##STR00665##

(234) To a 20 mL scintillation vial equipped with a magnetic stir bar were added C1050 (0.300 g, 0.286 mmol), phenoxydiphenylphosphine ([CAS 13360-92-4] 0.057 g, 0.300 mmol), PTSA (0.169 g, 0.886 mmol) and toluene (5 mL). The resulting reaction was allowed to stir for 60 minutes at ambient temperature, then it was filtered through a plug of silica gel, devolatilized and the resulting residue was recrystallized from toluene/heptanes at −35° C. The red/brown crystals were isolated by filtration, washed with toluene/heptanes (1:5, 2×10 mL) followed by heptanes (5 mL) then dried in vacuum to afford C947 (0.228 g, 84.2% yield).

(235) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 8.18 (d, J=7.5 Hz, 1H), 7.58 (d, J=7.7 Hz, 2H), 7.54 (t, J=7.4 Hz, 1H), 7.40 (t, J=7.6 Hz, 2H), 7.27-7.11 (m, 7H), 7.08-7.00 (m, 7H), 6.97 (d, J=7.3 Hz, 1H), 6.82 (t, J=7.8 Hz, 2H), 6.71 (t, J=7.3 Hz, 1H), 6.63 (s, 1H), 6.54 (d, J=8.3 Hz, 2H), 6.45 (s, 1H), 6.07 (s, 1H), 4.19-4.04 (m, 2H), 4.00-3.78 (m, 2H), 2.71 (s, 3H), 2.67 (s, 3H), 2.43 (s, 3H), 2.26 (s, 3H), 1.99 (s, 3H), 1.79 (s, 3H). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 127.9 (s).

Example 11

Synthesis of C609

(236) ##STR00666##

(237) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C601 (0.500 g, 0.833 mmol), 4,4″,4′″-phosphinidyntrismorpholine ([CAS 5815-61-2] 0.361 g, 1.25 mmol), and diethyl ether (20 mL). The resulting reaction was allowed to stir for 4 hours at 35° C. then cooled to ambient temperature. The resulting precipitate was isolated by filtration, washed with diethyl ether (2×10 mL), and dried in vacuum to afford C609 (0.420 g, 82.8% yield) as a pale red/brown powder.

(238) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) δ 16.69 (d, J=5.0 Hz, 1H), 7.36 (d, J=7.4 Hz, 1H), 7.20 (t, J=7.4 Hz, 1H), 6.82 (t, J=7.4 Hz, 1H), 6.59 (d, J=8.2 Hz, 1H), 4.81-4.70 (m, 1H), 3.52 (br s, 12H), 3.10 (br s, 12H), 1.72 (d, J=6.1 Hz, 6H). .sup.31P NMR (162 MHz, C.sub.6D.sub.6) δ 120.3 (s). .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 119.7 (s).

Example 12

Synthesis of C591

(239) ##STR00667##

(240) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C601 (0.500 g, 0.833 mmol), 4-(diphenylphosphino)morpholine (0.294 g, 1.08 mmol), and diethyl ether (20 mL). The resulting reaction was allowed to stir for 4 hours at 30° C. The resulting precipitate was isolated by filtration, washed with diethyl ether (2×10 mL), and dried in vacuum to afford C591 (0.302 g, 61.4% yield) as a pale red/brown powder.

(241) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 16.62 (d, J=5.8 Hz, 1H), 7.82-7.70 (m, 4H), 7.61 (t, J=7.8 Hz, 1H), 7.56 (d, J=7.6 Hz, 1H), 7.52-7.39 (m, 6H), 7.16 (d, J=8.5 Hz, 1H), 7.08 (t, J=7.5 Hz, 1H), 5.43-5.33 (m, 1H), 3.75-3.62 (m, 4H), 3.18 (m, 4H), 1.85 (d, J=6.1 Hz, 6H). .sup.31P NMR (162 MHz, CDCl.sub.3) δ 109.5 (s).

Example 13

Synthesis of C600

(242) ##STR00668##

(243) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C601 (0.500 g, 0.833 mmol), 4,4′-(phenylphosphinidene)bismorpholine (0.303 g, 1.08 mmol), and diethyl ether (20 mL). The resulting reaction was allowed to stir for 4 hours at 30° C. The resulting precipitate was isolated by filtration, washed with diethyl ether (2×10 mL), and dried in vacuum to afford C600 (0.422 g, 84.4% yield) as a pale red/brown powder.

(244) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 16.59 (d, J=5.2 Hz, 1H), 7.86-7.76 (m, 2H), 7.61 (t, J=8.0 Hz, 1H), 7.55 (d, J=7.6 Hz, 1H), 7.50-7.40 (m, 3H), 7.15 (d, J=8.4 Hz, 1H), 7.08 (t, J=7.6 Hz, 1H), 5.41-5.30 (m, 1H), 3.80-3.60 (m, 8H), 3.41-3.29 (m, 4H), 3.26-3.15 (m, 4H), 1.84 (d, J=6.2 Hz, 6H). .sup.31P NMR (162 MHz, CDCl.sub.3) δ 125.9 (br s).

Example 14

Synthesis of C590

(245) ##STR00669##

(246) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C601 (0.500 g, 0.833 mmol), 1-(diphenylphosphino)piperidine ([CAS 22859-54-7] 0.292 g, 1.08 mmol), and diethyl ether (20 mL). The resulting reaction was allowed to stir for 14 hours at 30° C. The resulting precipitate was isolated by filtration, washed with diethyl ether (2×10 mL), and then dissolved in a minimal amount of dichloromethane (4 mL). The solution was filtered through a pad of celite then hexanes (30 mL) was slowly added to afford a red precipitate. The solid was isolated by filtration, washed with hexanes (2×10 mL), and dried in vacuum to afford C590 (0.191 g, 38.9% yield) as a red solid.

(247) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 16.70 (d, J=5.7 Hz, 1H), 7.80-7.70 (m, 4H), 7.59 (t, J=7.8 Hz, 1H), 7.55 (d, J=7.7 Hz, 1H), 7.50-7.37 (m, 6H), 7.15 (d, J=8.4 Hz, 1H), 7.07 (t, J=7.5 Hz, 1H), 5.42-5.31 (m, 1H), 3.20-3.08 (m, 4H), 1.86 (d, J=6.1 Hz, 6H), 1.66-1.50 (m, 6H). .sup.31P NMR (162 MHz, CDCl.sub.3) δ 107.9 (s).

Example 15

Synthesis of C627 from C591

(248) ##STR00670##

(249) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C591 (0.250 g, 0.423 mmol), P426 (0.216 g, 0.507 mmol), and 10% toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90° C. for 5 hr. The resulting precipitate was isolated by filtration, washed with hexanes (2×10 mL) followed by methanol (2×10 mL), then dried in vacuum to afford C627 (0.146 g, 55.0% yield) as a green solid. The NMR data correspond to the data reported in the literature.

Example 16

Synthesis of C627 from C1050

(250) ##STR00671##

(251) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C1050 (0.5 g, 0.5 mmol), 2-isopropoxy-β-methylstyrene (0.18 g, 1.02 mmol), DCM (5 mL), and tosyl chloride (0.11 g, 0.57 mmol). The resulting reaction was heated to 60° C. for 30 min and then concentrated to dryness. The material was triturated with methanol (10 mL) and the resulting green solid was collected on a fritted funnel and washed with methanol (10 mL) followed by hexanes (10 mL) then dried in vacuum to afford C627 (0.268 g, 90% yield) as a green solid. The NMR data correspond to the data reported in the literature.

Example 17

Synthesis of C627 from C940

(252) ##STR00672##

(253) To a 40 mL scintillation vial equipped with a magnetic stirbar was added C940 (0.5 g, 0.53 mmol), 2-iso-propoxy-β-methylstyrene (0.18 g, 1.02 mmol), EtOAc (20 mL), and tosyl chloride (0.11 g, 0.58 mmol). The resulting reaction was heated to 60° C. for 30 min and then concentrated to dryness. The material was triturated with methanol (10 mL) and the resulting green solid was collected on a fritted funnel and washed with methanol (10 mL) followed by hexanes (10 mL) then dried in vacuum to afford C627 (0.177 g, 53% yield) as a green solid. The NMR data corresponded to the data reported in the literature.

Example 18

Synthesis of C627 from C609

(254) ##STR00673##

(255) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C609 (1.0 g, 1.64 mmol), P426 (0.805 g, 1.89 mmol), and 10% toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90° C. for 3 hr. The resulting precipitate was isolated by filtration and dissolved in DCM (10 mL). PTSA (0.343 g) was added to the solution and allowed to stir at room temperature for 30 min. The reaction mixture was concentrated and the C627 was triturated with MeOH (10 mL). The resulting precipitate was collected on a fritted funnel and washed with methanol (10 mL), then dried in vacuum to afford C627 (0.74 g, 72% yield) as a green solid. The NMR data corresponded to the data reported in the literature.

Example 19

Synthesis of C711 from C591

(256) ##STR00674##

(257) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C591 (0.250 g, 0.423 mmol), P510 (0.259 g, 0.507 mmol), and 10% toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90° C. for 5 hr. The resulting precipitate was isolated by filtration, washed with hexanes (2×10 mL) followed by methanol (2×10 mL), then dried in vacuum to afford C711 (0.224 g, 74.5% yield) as a green solid. The NMR data corresponded to the data reported in the literature.

Example 20

Synthesis of C627 from C609

(258) ##STR00675##

(259) To a 40 mL scintillation vial equipped with a magnetic stir bar was added C609 (1.0 g, 1.64 mmol), P510 (1.0 g, 1.96 mmol), and 10% toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90° C. for 5 hr. The resulting precipitate was isolated by filtration, washed with hexanes (2×10 mL) followed by methanol (2×10 mL), then dried in vacuum to afford C711 (0.64 g, 54.8% yield) as a green solid. The NMR data corresponded to the data reported in the literature.

Example 21

Synthesis of C829

(260) ##STR00676##

(261) To a THF solution (5 mL) of C787 (215 mg, 0.273 mmol) was added a THF solution (3 mL) of Cy.sub.2P(morph) (309.8 mg, 1.093 mmol) at r.t. The mixture was allowed to stir at ambient temperature for 15 min, leading to the quantitative formation of C829 as monitored in situ by .sup.31P NMR spectroscopy. The solvent was then removed under reduced pressure to afford a sticky solid. To this solid was added n-pentane (3×10 mL), and the resulting solid was removed by filtration. The combined n-pentane solutions were slowly concentrated by vapor diffusion into hexamethyldisiloxane at r.t. over 12 h, affording purple crystals of C829 (80 mg, 35%) which were isolated by filtration, washed with cold n-pentane, and dried under vacuum. FIG. 9 shows the ORTEP diagram of C829.

(262) .sup.1H NMR (300 MHz; C.sub.6D.sub.6): δ 20.52 (s, 1H), 8.47 (d, 2H, J.sub.H-H=10.6 Hz), 7.16 (t, 1H, J.sub.H-H=7.2 Hz), 7.00 (t, 2H, J.sub.H-H=7.5 Hz), 3.53 (t, 8H, J.sub.H-H=3.8 Hz), 2.82-2.76 (m, 8H), 1.98-1.12 (m, 44H). .sup.31P NMR (121 MHz; C.sub.6D.sub.6): δ 95.7 (s).

Example 22

Synthesis of C952

(263) ##STR00677##

(264) To a toluene solution (2 mL) of SIMes-HCl (34.7 mg, 0.101 mmol) was added solid KHMDS (20.2 mg, 0.101 mmol). The resulting mixture was allowed to stir at r.t. for 15 min, and then transferred into a toluene solution (5 mL) of C829 (79.8 mg, 0.096 mmol). The reaction was warmed up to 65° C. for 12 h. The resulting suspension was then passed through a short plug of Celite to remove the unwanted solid. All volatiles were removed under reduced pressure, affording a brown solid which was washed with cold n-pentane (10 mL). Further recrystallization from THF/pentane yielded brown/pink crystals of C852 (50 mg, 61%). FIG. 3 shows the ORTEP diagram of C852.

(265) .sup.1H NMR (300 MHz; C.sub.6D.sub.6): δ 19.56 (s, 1H), 9.13 (bs, 2H), 7.11-6.90 (m, 5H), 6.10 (bs, 2H), 3.45 (t, 4H, J.sub.H-H=4.3 Hz), 3.31-0.75 (m, 48H). .sup.31P NMR (121 MHz; C.sub.6D.sub.6): δ 92.2 (s).

Example 23

Synthesis of C907

(266) ##STR00678##

(267) To a THF solution (6 mL) of C765 (250 mg, 0.327 mmol) was added a THF solution (6 mL) of Cy.sub.2P(morph) (370.6 mg, 1.308 mmol) at ambient temperature. The mixture was allowed to stir at ambient temperature for 15 min, leading to the quantitative formation of C907 as monitored in situ by .sup.31P NMR spectroscopy. The solvent was then removed under reduced pressures to afford a brown oil. To this oil was added n-pentane (45 mL). The mixture was stirred at r.t. for 30 min, and the resulting solid was removed by filtration. The n-pentane solution was concentrated to ˜20 mL, and allowed to stand at −30° C. for 12 h, affording purple crystals of C807 (74 mg, 28%) which were isolated by filtration, washed with cold n-pentane, and dried under vacuum.

(268) .sup.1H NMR (300 MHz; C.sub.6D.sub.6): δ 19.81 (d, 1H, J.sub.H-H=11.2 Hz), 8.08 (d, 1H, J.sub.H-H=11.2 Hz), 3.60 (t, 8H, J.sub.H-H=3.7 Hz), 2.94 (t, 8H, J.sub.H-H=3.7 Hz), 2.07-0.91 (m, 54H). .sup.31P NMR (121 MHz; C.sub.6D.sub.6): δ 95.3 (s).

Example 24

Synthesis of C830

(269) ##STR00679##

(270) To a THF solution (2 mL) of C807 (50 mg, 0.062 mmol) was added a THF solution (2 mL) of SIMes-CHCl.sub.3 (26.4 mg, 0.062 mmol). The reaction was warmed up to 65° C. for 2 h. During the course of the reaction, the color changed from purple to brown. All volatiles were removed under reduced pressures, affording a brown solid. To this solid was added n-pentane (3×10 mL), and the resulting solid was removed by filtration. The combined n-pentane solution was slowly concentrated by vapor diffusion into hexamethyldisiloxane at r.t. over 12 h, affording brown crystals of C830 (18 mg, 35%) which were isolated by filtration, washed with Et.sub.2O, and dried under vacuum.

(271) .sup.1H NMR (300 MHz; C.sub.6D.sub.6): δ 19.03 (d, 1H, J.sub.H-H=11.3 Hz), 7.68 (d, 1H, J.sub.H-H=11.3 Hz), 6.85 (s, 2H), 6.57 (s, 2H), 3.53 (t, 4H, J.sub.H-H=2.9 Hz), 2.74 (s, 6H), 2.50 (s, 6H), 2.15 (s, 3H), 1.97 (s, 3H), 1.07-0.92 (m, 36H). .sup.31P NMR (121 MHz; C.sub.6D.sub.6): δ 90.3 (s).

Example 25

Synthesis of C903

(272) ##STR00680##

(273) To a THF solution (3 mL) of C765 (100 mg, 0.131 mmol) was added a THF solution (3 mL) of Cy.sub.2P(O.sup.iPr) ([CAS 65796-69-2]134.1 mg, 0.523 mmol) at ambient temperature. The mixture was allowed to stir at ambient temperature for 15 min, leading to the quantitative formation of the bis-phosphinite complex as monitored in situ by .sup.31P NMR spectroscopy (143.6 ppm). To this solution was added a THF solution (2 mL) of SIMes-CHCl.sub.3 (55.7 mg, 0.131 mmol). The resulting mixture was allowed to reflux at 65° C. for 2 h. The solvent was then removed under reduced pressures to afford a brown solid. To this solid was added n-pentane (10 mL). The mixture was stirred at r.t. for 5 min, and the resulting solid was removed by filtration. Slow evaporation of the n-pentane filtrate afforded brown crystals of C803 (71 mg, 68%) which were isolated by filtration, washed with cold n-pentane, and dried under vacuum. FIG. 4 shows the ORTEP diagram of C803.

(274) .sup.1H NMR (300 MHz; C.sub.6D.sub.6): δ 18.94 (d, 1H, J.sub.H-H=11.2 Hz), 7.57 (d, 1H, J.sub.H-H=11.2 Hz), 6.84 (s, 2H), 6.58 (s, 2H), 3.24-3.15 (m, 3H), 2.77 (s, 6H), 2.50 (s, 6H), 2.12 (s, 3H), 1.98 (s, 3H), 1.66-0.90 (m, 18H). .sup.31P NMR (121 MHz; C.sub.6D.sub.6): δ 151.0 (s).

Example 26

Synthesis of Olefin Metathesis Catalysts Represented by Formula (XI)

(275) ##STR00681##

(276) To a THF solution (2 mL) of the bispyridine complex C727 (100 mg, 0.138 mmol) was added 1.2 equivalent (0.165 mmol) of the corresponding PR.sup.1R.sup.2R.sup.3 ligand of Formula (II) in TH (1 mL). The resulting mixture was stirred at r.t. for 20 min. All volatiles were then removed under reduced pressures. Addition of pentane or diethyl ether led to a pink precipitate of the desired complex which was isolated by filtration and dried under vacuum.

(277) The olefin metathesis catalysts synthesized according to the procedure described in Example 26 are disclosed in Table 6. FIGS. 5, 6, 7, and 8 show the ORTEP diagrams of C850, C825, C832, and C865, respectively.

(278) TABLE-US-00006 TABLE 6 Olefin metathesis catalyst Quantity (mg) Yield (%) δ .sup.1H NMR (300 MHz; C.sub.6D.sub.6) δ .sup.31P NMR (121 MHz; C.sub.6D.sub.6) C852 110 94 19.56 (s, 1H), 9.13 (bs, 2H), 7.11-6.90 (m, 5H), 6.10 (bs, 2H), 3.45 (t, 4H, J.sub.H-H = 4.3 Hz), 3.31-0.75 (m, 48H) 92.2 (s) C855 79 67 19.30 (s, 1H), 8.03 (bs, 2H), 7.10-6.88 (m, 5H), 6.17 (bs, 2H), 3.27 (t, 16H, J.sub.H-H = 3.8 Hz), 2.75 (s, 6H), 2.69- 2.67 (m, 12H), 2.35 (s, 6H), 1.77 (s, 3H). 131.9 (s) C858 103 87 19.44 (s, 1H), 7.96 (bs, 2H), 7.00-6.92 (m, 5H), 6.15 (bs, 2H), 3.27-0.72 (m, 46H). 116.9 (s) C840 110 95 19.32 (s, 1H), 7.71 (d, 2H, J.sub.H-H = 8.5 Hz), 7.37 (t, 4H, J.sub.H-H = 7.5 Hz), 7.05-6.95 (m, 7H), 6.77 (t, 2H, J.sub.H-H = 7.5 Hz), 6.72 (s, 2H), 6.19 (s, 2H), 3.44-3.26 86.7 (s) (m, 6H), 2.68 (s, 6H), 2.58- 2.55 (m, 4H). 2.28 (s, 6H), 2.17 (s, 3H), 1.85 (s, 3H). C849 95 81 19.11 (s, 1H), 7.64 (d, 2H, J.sub.H-H = 5.9 Hz), 7.17 (t, 1H, J.sub.H-H = 6.8 Hz), 7.11-6.97 (m, 7H), 6.84 (t, 2H, J.sub.H-H = 8.8 Hz), 6.80 (s, 2H), 6.16 (s, 2H), 3.43-3.23 107.9 (s) (m, 12H), 2.73-2.65 (m, 11H). 2.26 (s, 6H), 2.22 (s, 3H), 2.08 (s, 3H), 1.82 (s, 3H) C850 93 80 19.65 (s, 1H), 9.30 (bs, 2H), 7.08-6.89 (m, 5H), 6.53 (bs, 2H), 3.30-0.77 (m, 54H). 92.1 (s) C825 101 89 19.55 (d, 1H, J.sub.H-H = 11.2 2H), 7.16-6.94 (m, 3H), 6.85 (s, 2H), 6.16 (bs, 2H), 4.18- 4.11 (m, 1H), 3.42-3.25 (m, 4H), 2.76 (s, 6H), 2.36 (s, 6H), 2.17 (s, 145.9 (s) 3H), 1.80 (s, 3H), 1.69-1.03 (m, 18H), 0.94 (d, 6H, J.sub.H-H = 5.9 Hz) C832 0 96 84 19.74 (d, 1H, J.sub.H-H = 11.2 Hz), 8.17 (bs, 2H), 7.10-6.88 (m, 5H), 6.65- 6.63 (m, 2H), 6.16 (bs, 2H), 6.11 (s, 2H), 3.44-3.26 (m, 4H), 2.75 (s, 6H), 2.36 (s, 6H), 2.19 (s, 92.0 (s) 3H), 1.80 (s, 3H), 1.58-0.93 (m, 22H). C865 89 75 19.53 (s, 1H), 8.24 (bs, 2H), 7.18-6.89 (m, 5H), 6.17 (bs, 2H), 4.06-4.01 (m, 1H), 3.43- 3.26 (m, 4H), 2.77 (s, 6H), 2.37 (s, 6H), 2.21 (s, 3H), 1.82 (s, 3H), 150.3 (s) 1.78-1.01 (m, 32H). C850n 82 54 (400 MHz; C.sub.6D.sub.6): δ 19.47 (s, 1H), 8.46 (bs, 1H), 7.14 (m, 1H), 7.01 (t, J = 7.7 Hz, 2H), 6.94 (s, 3H), 6.20 (m, 2H), 3.44- 3.17 (m, 4H), 3.04-2.75 (161.8 MHz; C.sub.6D.sub.6): δ 133.0 (s) (m, 11H), 2.75- 2.56 (s, 6H), 2.22 (s, 3H), 1.82 (s, 3H), 1.69-1.50 (m, 5H), 1.41 (s, 11H), 1.28 (s, 7H), 1.08- 0.75 (m, 3H). C851 92 78 (400 MHz; C.sub.6D.sub.6): δ 19.70 (s, 1H), 8.30 (bs, 2H), 7.19 (m, 1H), 7.04- 6.98 (m, 2H), 6.93 (s, 2H), 6.25 (s, 2H), 3.43- 3.16 (m, 4H), 2.86 (s, 6H), (161.8 MHz; C.sub.6D.sub.6): δ 118.7 (s) 2.85-2.77 (m, 12H), 2.48 (s, 6H), 222 (s, 3H), 182 (s, 3H), 1.48- 1.34 (m, 6H), 1.29 (m, 12H)

Catalytic Activity of Complexes

Example 27

RCM of Diethyl Diallylmalonate

(279) Ring closing metathesis reactions of diethyl diallylmalonate were run in the presence of different catalysts of the invention. In an argon filled glovebox, diethyl diallylmalonate (0.200 mL, 0.827 mmol), catalyst (0.021 mmol) and toluene (4 mL) were combined in a 40 mL scintillation vial equipped with a magnetic stir bar. The resulting reaction was stirred at 80° C. and analyzed by gas chromatography.

(280) TABLE-US-00007 entry catalyst time % yield 1 C609 1 15 2 3 30 3 5 36 4 20 50 5 C600 1 1 6 3 1 7 5 1 8 20 1 9 C591 1 3 10 3 5 11 5 6 12 20 9

Example 28

Vinyl Ether Quenching Experiments

(281) The catalysts of the invention show fast initiation, as indicated by the vinyl ether quenching experiments. For example, the initiation rate of the C932 complex is about two orders of magnitude faster than the C849 analogue.

(282) ##STR00695##
FIG. 10 shows the vinyl ether quenching experiments for catalysts: C849, C865, C825, C850, C852, and C832. FIG. 11 shows the vinyl ether quenching experiments for catalysts: C831, C840, C849, and C858. FIG. 12 shows the vinyl ether quenching experiments for catalysts: C848, C852, C855, and C858.

Example 29

ROMP Reactions

(283) The catalytic activity of the complexes according to the invention, was evaluated in ROMP reactions as follows. A 250 mL beaker was filled with 100 g of DCPD-HT monomer and 50 ppm of CHP (cumene hydroperoxide). The monomer was equilibrated to the desired temperature in an oil bath (30° C.+/−0.5° C.). A J-Type thermocouple was suspended directly into the center of the monomer. The catalyst under study was dissolved in solvent (either toluene or CH.sub.2Cl.sub.2) to form a catalyst solution and the catalyst solution was then added to the monomer at a molar ratio of 45,000:1 (monomer:catalyst) to form a ROMP composition. Addition of the catalyst to the monomer to form the ROMP composition denoted the start of the ROMP reaction and hence, this was time point zero. Temperature readings were recorded using the thermocouple. The exotherm time was determined by measuring the amount of time that passed (i.e., the time difference) between time point zero and the time point that a propagating interface of the ROMP composition was first visually observed as the ROMP composition transitioned from a liquid state or gel state to a cured polymer state. ROMP reactions were stopped 2 hours after addition of the catalyst solution to the monomer. Time to exotherm is expressed by: slow >120 minutes; moderate 30-120 minutes; medium 1-<30 minutes; fast <1 minute and peak exotherm temperature are shown in Table 7.

(284) TABLE-US-00008 TABLE 7 DCPD-HT Monomer Time to Exotherm Peak Exotherm Catalyst Temperature (° C.) (min.) Temperature (° C.) C931 30 medium 192 C940 30 moderate 192 C949morph 30 moderate 192 C958 30 moderate 188 C949 30 slow 186 00