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

Journal of the American Chemical Society

PubMedID: 22329633

Brown ZD, Vasko P, Fettinger JC, Tuononen HM, Power PP. A germanium isocyanide complex featuring (n ? p*) back-bonding and its conversion to a hydride/cyanide product via C-H bond activation under mild conditions. J Am Chem Soc. 2012;134(9):4045-8.
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 ? p* 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 p* 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.