6533b85bfe1ef96bd12ba149
RESEARCH PRODUCT
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
James C. FettingerPhilip P. PowerZachary D. BrownPetra VaskoHeikki M. Tuononensubject
Models MolecularC h bondCyanidesLigandHydrideGermaniumIsocyanideCyanidechemistry.chemical_elementGermaniumHydrogen BondingGeneral ChemistryPhotochemistryCrystallography X-RayBiochemistryMedicinal chemistryCatalysisAdductchemistry.chemical_compoundColloid and Surface ChemistrychemistryOrganometallic Compoundsta116Pi backbondingHydrogendescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2012-02-15 | Journal of the American Chemical Society |