A germanium isocyanide complex featuring (n → π*) back-bonding and its conversion to a hydride/cyanide product via C-H bond activation under mild conditions

J Am Chem Soc. 2012 Mar 7;134(9):4045-8. doi: 10.1021/ja211874u. Epub 2012 Feb 22.

Abstract

Reaction of the diarylgermylene Ge(Ar(Me(6)))(2) [Ar(Me(6)) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(CH(3))(3))(2)] with tert-butyl isocyanide gave the Lewis adduct species (Ar(Me(6)))(2)GeCNBu(t), in which the isocyanide ligand displays a decreased C-N stretching frequency consistent with an n → π* back-bonding interaction. Density functional theory confirmed that the HOMO is a Ge-C bonding combination between the lone pair of electrons on the germanium atom and the C-N π* orbital of the isocyanide ligand. The complex undergoes facile C-H bond activation to produce a new diarylgermanium hydride/cyanide species and isobutene via heterolytic cleavage of the N-Bu(t) bond.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Crystallography, X-Ray
  • Cyanides / chemistry*
  • Germanium / chemistry*
  • Hydrogen / chemistry*
  • Hydrogen Bonding
  • Models, Molecular
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*

Substances

  • Cyanides
  • Organometallic Compounds
  • Germanium
  • Hydrogen