Tenn, William J., III and Conley, Brian L. and Hovelmann, Claas H. and Ahlquist, Marten and Nielsen, Robert J. and Ess, Daniel H. and Oxgaard, Jonas and Bischof, Steven M. and Goddard, William A., III and Periana, Roy A. (2009) Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV). Journal of the American Chemical Society, 131 (7). pp. 2466-2468. ISSN 0002-7863 http://resolver.caltech.edu/CaltechAUTHORS:20090803-105400064
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We report that SeO_2 catalyzes the facile oxy-functionalization of (CO)_5Re(I)-Me^(δ−) with IO_4− 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 CH_3Se(VI) species. Furthermore, (CO)_3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO_2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M−R^(δ−) polarized bonds.
|Additional Information:||© 2009 American Chemical Society. Received September 10, 2008. We thank Chevron Company and Scripps Florida for financial support, Prof. William C. Kaska for helpful suggestions, and Ariana Nussdorf for work on kinetic analysis. M.A. acknowledges The Knut and Alice Wallenberg Foundation. This work was supported by a fellowship within the Postdoc-Programme of the German Academic Exchange Service (DAAD) supporting C.H.H. Supporting Information Available: Synthetic procedures, experimental and computational details. This material is available free of charge via the Internet at http://pubs.acs.org.|
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|Deposited By:||Tony Diaz|
|Deposited On:||21 Aug 2009 20:36|
|Last Modified:||26 Dec 2012 11:07|
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