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Article

Intramolecular Oxygen Transfer from Nitro Groups to CC Bonds Mediated by Iridium Hydrides

Supporting Info

Xingwei Li, Christopher D. Incarvito, Tiffany Vogel, and Robert H. Crabtree*

Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107

Organometallics, 2005, 24 (13), pp 3066–3073

DOI: 10.1021/om050116+

Publication Date (Web): May 14, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

The functionalized alkynes o-RCC(C₆H₄)NO₂ (R = H or alkyl) formally insert into two iridium hydrides, during which O-transfer of the nitro group into the CC bond of o-RCC(C₆H₄)NO₂ is observed. For the terminal alkyne with R = H, iridium(III) nitroso complexes were isolated. For internal alkynes with R = Me or ⁿPr, iridium hydride anthranil complexes were obtained as a result of O-transfer with a different regiochemistry. Mechanisms for these transformations, including a previously unknown O-transfer step from the nitro to the RCC bond, are proposed.