Oxy-Functionalization of Nucleophilic Rhenium(I) Metal Carbon Bonds Catalyzed by Selenium(IV)

• Published in: Journal of the American Chemical Society Vol. 131; no. 7; pp. 2466 - 2468
• Main Authors: Tenn, William J, Conley, Brian L, Hövelmann, Claas H, Ahlquist, Mårten, Nielsen, Robert J, Ess, Daniel H, Oxgaard, Jonas, Bischof, Steven M, Goddard, William A, Periana, Roy A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 25-02-2009
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/ja806814c

We report that SeO2 catalyzes the facile oxy-functionalization of (CO)5Re(I)-Meδ− with IO4 − to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH3Se(VI) species. Furthermore, (CO)3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M−Rδ− polarized bonds.