Preparation and Molecular and Electronic Structures of Iron(0) Dinitrogen and Silane Complexes and Their Application to Catalytic Hydrogenation and Hydrosilation

Suzanne C. Bart, Emil Lobkovsky, and Paul J. Chirik*
Contribution from the Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853
J. Am. Chem. Soc., 2004, 126 (42), pp 13794–13807
DOI: 10.1021/ja046753t
Publication Date (Web): October 5, 2004
Copyright © 2004 American Chemical Society
*

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

, pc92@cornell.edu

Abstract

Abstract Image

Reduction of the five-coordinate iron(II) dihalide complexes (iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe2)2C6H3NCMe)2C5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, (iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2). Both dinitrogen compounds serve as effective precatalysts for the hydrogenation and hydrosilation of olefins and alkynes. Effecient catalytic reactions are observed with low catalyst loadings (≤0.3 mol %) at ambient temperature in nonpolar media. The catalytic hydrosilations are selective in forming the anti-Markovnikov product. Structural characterization of a high spin iron(0) alkyne and a bis(silane) σ-complex has also been accomplished and in combination with isotopic labeling studies provides insight into the mechanism of both catalytic C−H and catalytic C−Si bond formation.

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History

  • Published In Issue October 27, 2004
  • Received June 2, 2004

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