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Multiple C−H Activations of Methyltert-Butyl Ether at Pincer Iridium Complexes: Synthesis and Thermolysis of Ir(I) Fischer Carbenes

Romero, Patricio E. and Whited, Matthew T. and Grubbs, Robert H. (2008) Multiple C−H Activations of Methyltert-Butyl Ether at Pincer Iridium Complexes: Synthesis and Thermolysis of Ir(I) Fischer Carbenes. Organometallics, 27 (14). pp. 3422-3429. ISSN 0276-7333. doi:10.1021/om8003515. https://resolver.caltech.edu/CaltechAUTHORS:20170308-131108769

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Abstract

The C−H activation of methyl tert-butyl ether (MTBE) mediated by pincer iridium complexes derived from PNP and PCP frameworks has been studied. Double C−H activation of MTBE by these complexes leads to formation of Ir(I) Fischer carbenes of the type (pincer)Ir═C(H)OtBu via elimination of H_2. In one case, the structure of the Fischer carbene has been confirmed by single-crystal X-ray analysis. For both systems, the carbenes are obtained as kinetic products, and prolonged thermolysis leads to the formation of thermodynamically stable trans-(pincer)Ir(H)_2(CO) complexes. A mechanism for this transformation is presented along with reactivity studies supporting the proposal.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om8003515DOIArticle
http://pubs.acs.org/doi/abs/10.1021/om8003515PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om8003515Related ItemSupporting Information
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2008 American Chemical Society. Received 19 April 2008. Published online 2 July 2008. Published in print 1 July 2008. This work was supported by BP chemicals under the MC^2 initiative. M.T.W. acknowledges the Moore Foundation for a graduate fellowship. Dr. Michael Day and Larry Henling are acknowledged for crystallographic analysis.
Funders:
Funding AgencyGrant Number
BP MC2 programUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Issue or Number:14
DOI:10.1021/om8003515
Record Number:CaltechAUTHORS:20170308-131108769
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170308-131108769
Official Citation:Multiple C−H Activations of Methyl tert-Butyl Ether at Pincer Iridium Complexes: Synthesis and Thermolysis of Ir(I) Fischer Carbenes Patricio E. Romero, Matthew T. Whited, and Robert H. Grubbs Organometallics 2008 27 (14), 3422-3429 DOI: 10.1021/om8003515
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74910
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:08 Mar 2017 21:48
Last Modified:15 Nov 2021 16:29

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