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Synthesis, Structure, and Reactivity of a Rhenium Oxo-Vinylalkylidene Complex

Flatt, Brenton T. and Grubbs, Robert H. and Blanski, Rusty L. and Calabrese, Joseph C. and Feldman, Jerald (1994) Synthesis, Structure, and Reactivity of a Rhenium Oxo-Vinylalkylidene Complex. Organometallics, 13 (7). pp. 2728-2732. ISSN 0276-7333.

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The reaction of 3 equiv of KOC(CF_3)_2Me with ReOCl_3(PPh_3)_2 in dichloromethane, followed by recrystallization from hexanes/THF, gives ReO[OC(CF_3)_2Me]_3(THF)_2( 1) in 35 7% yield. An X-ray diffraction study of 1 (monoclinic, P2_1/n, a = 10.010(3) Å, b = 29.247(6) Å, c = 10.800(3) Å, β = 117.09(1)', Z = 4) reveals a facial arrangement of the three alkoxide ligands around the metal center in a distorted octahedron. The ligand environment in 1 is quite crowded, as evidenced by an elongated Re-O bond between rhenium and one of the THF ligands. The reaction of 3,3-diphenylcyclopropene with 1 in dichloromethane gives initially a mixture of two isomeric rhenium oxo-vinylalkylidene complexes, of which the isomer syn,mer-ReO[C(H)-CH=CPh_2] [OC(CF3)2Me]3(THF) (2b) was isolated in 87% yield. An X-ray diffraction study of 2b (triclinic, P1^(bar), a = 10.459(3) Å, b = 10.913(3) Å, c = 21.308(6) Å, α = 91.16(3)°,β = 102.05-(2)°, γ = 117.98(2)°, 2 = 2) supports a pseudooctahedral structure with mutually trans vinylalkylidene and THF ligands. Complex 2b does not react readily with internal or terminal olefins; however, the addition of GaBr_3 (1 equiv) to 2b yields moderately active catalyst(s) that metathesize cis-2-pentene at ~6.7 turnovers min^(-1). No propagating alkylidene species are observed during the metathesis reaction.

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Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 1994 American Chemical Society. Received February 14, 1994. Financial support from the National Science Foundation and DuPont is gratefully acknowledged. B.T.F. thanks Caltech for an Institute Fellowship. We thank S. T. Nguyen and Drs. R. A. Paciello, L. K. Johnson, M. R. Gagné, and C. Fraser for many helpful discussions and N. Jones and W. Marshall for assistance with the X-ray structure determinations.
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Caltech Division of Chemistry and Chemical Engineering8927
Issue or Number:7
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Official Citation:Synthesis, Structure, and Reactivity of a Rhenium Oxo-Vinylalkylidene Complex Brenton T. Flatt, Robert H. Grubbs, Rusty L. Blanski, Joseph C. Calabrese, and Jerald Feldman Organometallics 1994 13 (7), 2728-2732 DOI: 10.1021/om00019a032
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86503
Deposited By: George Porter
Deposited On:21 May 2018 20:16
Last Modified:03 Oct 2019 19:44

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