title: 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.
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.
authors.affiliation: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, USA.
authors.forename: Zachary D
authors.initials: ZD
authors.lastname: Brown
authors.forename: Petra
authors.initials: P
authors.lastname: Vasko
authors.forename: James C
authors.initials: JC
authors.lastname: Fettinger
authors.forename: Heikki M
authors.initials: HM
authors.lastname: Tuononen
authors.forename: Philip P
authors.initials: PP
authors.lastname: Power
mesh_terms: D018360:Crystallography, X-Ray; D003486:Cyanides / Q000737:chemistry*; D005857:Germanium / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D003486:Cyanides; D009942:Organometallic Compounds; D005857:Germanium; D006859:Hydrogen