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Volumn 117, Issue 20, 1995, Pages 5503-5511

Reactions of Ruthenium Carbenes of the Type (PPh3)2(X)2Ru=CH-CH=CPh2 (X = Cl and CF3COO) with Strained Acyclic Olefins and Functionalized Olefins

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EID: 0001698392     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00125a010     Document Type: Article
Times cited : (244)

References (51)
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    • However, these do not exhibit metathesis activity in our hands and in the hands of others, see ref lb
    • Bohle, D. S.; Clark, G. R.; Rickard, C. E. F.; Roper, W. R.; Wright, L. J. J. Organomet. Chem. 1988, 358, 411–447. However, these do not exhibit metathesis activity in our hands and in the hands of others, see ref lb.
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    • For example, the following have been observed: (i) The increase in steric bulk of the phosphine ligand enhances the metathesis reactivity of 1 (ref 1c). (ii) The presence of excess phosphine slows down the rate of metathesis, and the rate of the reaction was greatly accelerated when one of the phosphines was removed by complexing with copper chloride
    • For example, the following have been observed: (i) The increase in steric bulk of the phosphine ligand enhances the metathesis reactivity of 1 (ref 1c). (ii) The presence of excess phosphine slows down the rate of metathesis, and the rate of the reaction was greatly accelerated when one of the phosphines was removed by complexing with copper chloride.(a) Benedicto, A. D.; Grubbs, R. H. Unpublished results.
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    • The sterically preferred coordination site located trans to the carbene is apparent from a Chem3D three-dimensional space-filling drawings of 8 based on its crystal structure data. Coordination sites that are trans to the carbenes have also been observed in certain rhenium and tantalum alkylidene complexes. For detail discussions, see:(a) Wallace, K. C.; Davis, W. M.; Schrock, R. R. Inorg. Chem. 1990, 29, 1104–1106.
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    • The general decomposition pathways for alkylidene complexes usually involve (i) rearrangement of alkylidenes to olefins (for Nb and Ta). (ii) rearrangement of metallacyclobutane to olefins via β-hydride elimination, and (iii) bimolecular coupling of alkylidenes to give olefins. For detail discussions, see:(a) Feldman, J.; Schrock, R. R. Prog. Inorg. Chem. 1991, 39, 1—74.
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    • Recent work in our group has indicated that the active species in this system may indeed be a monophosphine complex See also ref 6
    • Recent work in our group has indicated that the active species in this system may indeed be a monophosphine complex: Dias, E. L.; Grubbs, R. H. Unpublished results. See also ref 6.
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