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, Paul J. Chirik

Research output: Contribution to journalArticle

601 Scopus citations

Abstract

Reduction of the five-coordinate iron(II) dihalide complexes ( iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe 2)2C6H3N=CMe)2C 5H3N; 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) 2. 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.

Original languageEnglish (US)
Pages (from-to)13794-13807
Number of pages14
JournalJournal of the American Chemical Society
Volume126
Issue number42
DOIs
StatePublished - Oct 27 2004
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation'. Together they form a unique fingerprint.

  • Cite this