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Synthesis, Molecular Structure, and Racemate−Meso Interconversion for rac-(Me_2Si)_2{η^5-C_5H-3-(CHMe_2)-5-Me}_2MCl_2 (M = Ti and Zr)

Miyake, Shigenobu and Henling, Lawrence M. and Bercaw, John E. (1998) Synthesis, Molecular Structure, and Racemate−Meso Interconversion for rac-(Me_2Si)_2{η^5-C_5H-3-(CHMe_2)-5-Me}_2MCl_2 (M = Ti and Zr). Organometallics, 17 (25). pp. 5528-5533. ISSN 0276-7333. doi:10.1021/om980505m.

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Doubly [SiMe_2]-bridged group IV metallocenes, rac-(Me_2Si)_2{η^5-C_5H-3-(CHMe_2)-5-Me}_2MCl_2 (M = Ti, Zr), have been synthesized, and a crystal structure of rac-(Me_2Si)_2{η^5-C_5H-3-(CHMe_2)-5-Me}_2TiCl_2 has been determined by X-ray diffraction methods. Racemate−meso interchange occurs in benzene solution just above room temperature, affording an approximately 1:1 mixture of rac-(Me_2Si)_2{η^5-C_5H-3-(CHMe_2)-5-Me}_2TiCl_2 and meso-(Me_2Si)_2{η^5-C_5H-3-(CHMe_2)-5-Me}_2TiCl_2. Measurements of the kinetics of the approach to equilibrium reveal ΔH^⧧ = 18(1) kcal·mol^(-1) and ΔS^⧧ = −7(2) eu. The corresponding zirconium compound is configurationally stable.

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Additional Information:© 1998 American Chemical Society. Received June 18, 1998. The work has been supported by the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431), Exxon Chemicals America, and Japan Polyolefins Co., Ltd. S.M. is grateful for a fellowship by Japan Polyolefins Co., Ltd. The authors wish to thank Dr. Dario Veghini for useful discussions.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG03-85ER13431
Exxon Chemicals AmericaUNSPECIFIED
Japan Polyolefins Co., Ltd.UNSPECIFIED
Issue or Number:25
Record Number:CaltechAUTHORS:20180518-154132453
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Official Citation:Synthesis, Molecular Structure, and Racemate−Meso Interconversion for rac-(Me2Si)2{η5-C5H-3-(CHMe2)-5-Me}2MCl2 (M = Ti and Zr) Shigenobu Miyake, Lawrence M. Henling, and John E. Bercaw Organometallics 1998 17 (25), 5528-5533 DOI: 10.1021/om980505m
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86473
Deposited By: George Porter
Deposited On:21 May 2018 15:26
Last Modified:15 Nov 2021 20:39

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