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Stereoselective Decarbonylation of Methanol to Form a Stable Iridium(III) trans-Dihydride Complex

Supporting Info

Susan M. Kloek, D. Michael Heinekey,* and Karen I. Goldberg*

Department of Chemistry, Box 351700, University of Washington, Seattle, Washington 98195-1700

Organometallics, 2006, 25 (12), pp 3007–3011

DOI: 10.1021/om051098z

Publication Date (Web): May 5, 2006

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

Thermolysis of the known cationic iridium complex [(PNP)Ir(C₆H₅)H]PF₆ (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) in methanol results in reductive elimination of benzene and stereoselective methanol decarbonylation to form the new iridium(III) trans-dihydride carbonyl complex [(PNP)Ir(CO)H₂]PF₆ (trans-2). The iridium(III) dihydride complex [(PNP)Ir(H)₂]PF₆ (3) is formed as a minor product. cis-[(PNP)Ir(CO)H₂]PF₆ (cis-2) has been independently prepared by the reaction of dihydride 3 with CO and undergoes reductive elimination of hydrogen at room temperature to form the iridium(I) carbonyl [(PNP)Ir(CO)]PF₆ (4), demonstrating that cis-2 is not an intermediate in the decarbonylation reaction.

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Published In Issue June 05, 2006
Received December 28, 2005

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Article

Stereoselective Decarbonylation of Methanol to Form a Stable Iridium(III) trans-Dihydride Complex