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Published November 12, 2008 | Supplemental Material
Journal Article Open

A catalytic cycle for oxidation of tert-butyl methyl ether by a double C−H activation-group transfer process


A square-planar, iridium(I) carbene complex is shown to effect atom and group transfer from nitrous oxide and organic azides, releasing the corresponding formate or formimidate and an iridium(I)−dinitrogen adduct. The dinitrogen complex performs C−H activation upon photolysis or thermolysis, regenerating the carbene from tert-butyl methyl ether with loss of H_2. Taken together, these reactions represent a net catalytic cycle for C−H functionalization by double C−H activation to generate metal−carbon multiple bonds. Additionally, the unusual group transfer from diazo reagents underscores the unique nature of the reactivity observed for nucleophilic-at-metal carbene complexes.

Additional Information

© 2008 American Chemical Society. Received September 9, 2008. Prof. Oleg Ozerov (Brandeis University) is acknowledged for stimulating discussions. Larry Henling (Caltech) assisted with crystallographic analysis. Generous financial support of this research was provided by the Moore Foundation (fellowship to M.T.W.) and BP (MC2 initiative). Detailed experimental procedures and characterization data. Crystallographic details for 3 are provided in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

Attached Files

Supplemental Material - ja8071385_si_001.pdf

Supplemental Material - ja8071385_si_002.cif


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