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Synthesis and Investigation of Homo- and Heterobimetallic Ruthenium Olefin Metathesis Catalysts Exhibiting Increased Activities

Dias, Eric L. and Grubbs, Robert H. (1998) Synthesis and Investigation of Homo- and Heterobimetallic Ruthenium Olefin Metathesis Catalysts Exhibiting Increased Activities. Organometallics, 17 (13). pp. 2758-2767. ISSN 0276-7333. http://resolver.caltech.edu/CaltechAUTHORS:20180518-142549205

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Abstract

The previously reported ruthenium carbenes (PCy_3)_2Cl_2RuCHR (R = CHCPh_2 (1a), Ph (1b)) react with the bridged-chloride dimers [(p-cymene)RuCl_2]_2, [(p-cymene)OsCl_2]_2, and [(tBu_2Cp)RhCl_2]_2 to quantitatively form the bimetallic, bridged-chloride ruthenium carbenes 2a,b, 4a,b, and 6a,b and 1 equiv of each corresponding piano-stool complex. In the ring-opening metathesis polymerization of 1,5-cyclooctadiene, catalyst activity was found to increase in the order M = Ru < Os < Rh for the ancillary metal centers, with all of the bimetallic catalysts having higher activities than 1a,b. The kinetics of ROMP of the derivatized norbornene 9 were studied using catalyst 2a, and the data support an associative mechanism of olefin metathesis, contrary to the mechanism of olefin metathesis proposed for the parent catalysts 1a,b.


Item Type:Article
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https://dx.doi.org/10.1021/om9708788DOIArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 1998 American Chemical Society. Received October 10, 1997. Financial support has been provided by Rohm and Haas and the National Institute of Health.
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Rohm and Haas CompanyUNSPECIFIED
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Record Number:CaltechAUTHORS:20180518-142549205
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180518-142549205
Official Citation:Synthesis and Investigation of Homo- and Heterobimetallic Ruthenium Olefin Metathesis Catalysts Exhibiting Increased Activities Eric L. Dias and Robert H. Grubbs Organometallics 1998 17 (13), 2758-2767 DOI: 10.1021/om9708788
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86463
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:21 May 2018 15:47
Last Modified:21 May 2018 15:47

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