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Published July 28, 2008 | Supplemental Material
Journal Article Open

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

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.

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.

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August 19, 2023
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