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. https://resolver.caltech.edu/CaltechAUTHORS:20180518-154132453
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Abstract
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. | |||||||||
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| Issue or Number: | 25 | |||||||||
| DOI: | 10.1021/om980505m | |||||||||
| Record Number: | CaltechAUTHORS:20180518-154132453 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180518-154132453 | |||||||||
| 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 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 21 May 2018 15:26 | |||||||||
| Last Modified: | 15 Nov 2021 20:39 |
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