Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Patent
1997-05-23
1999-10-19
Nazario-Gonzalez, Porfirio
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
556 22, 556136, C07F 928, C07F 1500
Patent
active
059691700
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 strained and 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 substituent 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 substituent group 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, depolymerization of unsaturated polymers and synthesis of telechelic 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.
Burrell et al., Synthesis and Reactions of Ru(=CH.sub.2) C1 (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 C1 (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-Oxanorbornene Derivatives Using Ruthenium Catalysts", 1990, pp. 525-536.
Novak et al., "Catalytic Organometalic Chemistry in Water: The Aqueous Ring-Opening Metathesis Polymerization of 7-Oxanorbornene Derivatives", 1988, JACS, vol.110,pp. 7542-43g.
Novak et al., "The Ring Opening Metathesis Polymerization of 7-Oxabicyclo [2.2.2] hept-5-ene Derivatives: A New Acyclic Polymeric Ionophere", 1988, JACS, vol.110,pp.960-961].
Hillmyer et al., "The Aqueous Ring-Opening Metathesis Polymerization of exo-N-Methyl-7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarbonximide" 1991,pp. 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 Norbornene 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 RuHC1(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), p. 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.
Grubbs Robert H.
Johnson Lynda K.
Nguyen Sonbinh T.
California Institute of Technology
Nazario-Gonzalez Porfirio
LandOfFree
High activity ruthenium and osmium metal carbene complexes for o does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with High activity ruthenium and osmium metal carbene complexes for o, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and High activity ruthenium and osmium metal carbene complexes for o will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2057493