Polymer depolymerization using ruthenium and osmium carbene comp

Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By c content reduction – e.g. – cracking – etc.

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585832, 585645, 585505, 585509, 585511, 585514, 585538, 585600, 585601, 585627, 585654, 585665, 525938, 576171, C08F 850

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057289174

ABSTRACT:
Disclosed are ruthenium and osmium carbene compounds which are stable in the presence of a variety of functional groups and which can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins. Specifically, the present invention relates to carbene compounds of the formula ##STR1## wherein: M is Os or Ru; R and R.sup.1 are independently selected from hydrogen and functional groups C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.2 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl or C.sub.1 -C.sub.20 alkylsulfinyl; each optionally substituted with C.sub.1 -C.sub.5 alkyl, a halogen, C.sub.1 -C.sub.5 alkoxy or with a phenyl group optionally substituted with a halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; X and X.sup.1 are independently selected from any anionic ligand; and L and L.sup.1 are each trialkyl phosphine ligands where at least one of the alkyl groups on the phosphine is a secondary alkyl or a cycloalkyl. A broad array of metathesis reactions are enabled including ring-opening metathesis polymerization of cyclic olefins, ring closing metathesis of acyclic dienes, cross metathesis involving at least one acyclic or unstrained cyclic olefin, and depolymerization of unsaturated polymers.

REFERENCES:
patent: 4883851 (1989-11-01), Grubbs et al.
patent: 4945135 (1990-07-01), Grubbs et al.
patent: 4945144 (1990-07-01), Grubbs et al.
patent: 5198511 (1993-03-01), Brown-Wensley et al.
patent: 5296566 (1994-03-01), Brown-Wensley et al.
patent: 5312940 (1994-05-01), Grubbs et al.
patent: 5342909 (1994-08-01), Grubbs et al.
Hawley's Condensed Chemical Dictionary, Eleventh Edition, Van Nostrand Reinhold, New York, pp. 613, 614, and 854, 1987.
Burrell et al., "Synthesis and Reactions of Ru(=CH.sub.2) Cl (No).sub.2, A Stable Terminal MethyleneComplex and the Crystal Structure of Ru(CH.sub.2 PPF.sub.2).sub.2 (n.sup.2 -C.sub.2 F.sub.4 Cl (N)) (PPH.sub.3)", J. Chem. Soc., Dalton Trans., 1991, pp. 609-614.
Ivin, K.J. "Olefin Metathesis", 1983, Academic Press, pp. vii-x, 34-36.
McGrath et al., "Aqueous Ring-Opening Metathesis Polymerization of 7-Oxanorborene Derivatives Using Ruthenium Catalysts", 1990, pp. 525-536.
Novak et al., "Catalytic Organometalic Chemistry in Water: The Aqueous Ring-Opening Metathesis Polymerization of 7-Oxanorborene Derivatives", 1988, JACS, vol.110, pp. 7542-7543g.
Novak et al., "The Ring Opening Metathesis Polymerization of 7-Oxabicyclo JACS, vol.110,pp.960-961!.
Hillmyer et al., "The Aqueous Ring-Opening Metathesis Polymerization of 162-163.
Carter et al., "Review of the Chemistry of Cyclopropane Compounds", Apr. 20, 1964,pp. 497-525.
Schmidbaur et al., "Ylide Chemistry: An Account of Structural, Conformational and Redox Investigations" 1983m pp. 167-170.
"Metathesis of Functionalized Olefin", J. of Molecules Catalysis, 15 (1982), pp. 35-45.
Collman et al., Radical Mechanism for the Decomposition of RuOEP (CH.sub.2 CH.sub.3).sub.2. Determination of the Metal-Carbon Bond Dissociation Energy, J. AM. Soc. vol. 198, pp. 1332-1333 (1986).
Bruce et al., "Cyclopentadienyl-Ruthenium and -osmium Chemistry. Some Reactions ofSubstituted Vinylidene Complexes," J. Organometallic Chem. 171: C5-C8 (1979).
M.H.L. Green et al., "Carbene Complexes of Iron, Molybdenum, and Ruthenium: A NewRoute to Metal-Carbene Derivatives," J. Chem. Soc. (A) 794-797 (1971).
H. Le Bozec et al., "A New Route to Vinylcarbene Metal Complexes in One Step from2-Propyn-1-ols and Arene Ruthenium (.parallel.) Derivatives," J. Chem. Soc. Chem. Comm. 219-221(1989).
Nguyen et al., "Ring-Opening Metathesis Polymerization (ROMP) of Norborene by a GroupVIII Carbene Complex in Protic Media," J. Am. Chem. Soc. 114: 3974-3975 (1992).
Grundy et al., "Migratory-Insertion Reactions of Osmium (II) Ethyl Complexes DerivedFrom an Osmium (0) Ethylene Complex," J. Organometallic Chem. 216:255-262 (1981).
Grundy et al., "Propionyl Complexes of Ruthenium Derived From the Reaction of Ethylenewith RuHCl (CO).sub.2 (PPh.sub.3).sub.2 " J. Organometallic Chem. 265:77-85 (1984).
Richard R. Schrock, "Living Ring-Opening Metathesis Polymerization Catalyzed by Well-Characterized Transition-Metal Alkylidene Complexes", Acc.Chem.Res. 1990, vol. 23, pp. 158-165.
Gregory C. Fu et al., "Catalytic Ring-Closing Metathesis of Functionalized Dienes by a Ruthenium Carbene Complex" Am. Chem Soc. 1993, pp. 9856-9857.
Robert H. Grubbs et al., "Ring-Opening Metathesis Polymerization Catalysts" Polymer Preprints 1994, 35(1), pp. 688.
Marc. A. Hillmyer et al., "The ROMP of COD by a Well-Defined Metathesis Catalyst in the Presence of a Difunctional Chain Transfer Agent: The Preparation of Hydroxy-Telechelic 1,4-Poly(butadiene)". Polymer Preprints 1993, 34(2), pp. 388-389.
Marc A. Hillmyer et al. "Preparation of Hydroxytelechelic Poly(butadiene) via Ring-Opening Metathesis Polymerization Employing a Well-Defined Metathesis Catalyst" Am. Chem Soc. Macromolecules, vol. 26, No. 4, 1992, pp. 872-874.
SonBinh R. Nguyen et al. "Syntheses and Activities of New Single-Component Ruthenium-Based Olefin Metathesis Catalysts" J. Am. Chem Soc. 1993, 115, 9858-9859.

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