title: Mechanistic study of stepwise methylisocyanide coupling and C-H activation mediated by a low-valent main group molecule.
abstract: An experimental and DFT investigation of the mechanism of the coupling of methylisocyanide and C-H activation mediated by the germylene (germanediyl) Ge(Ar(Me6))2 (Ar(Me6) = C6H3-2,6(C6H2-2,4,6-Me3)2) showed that it proceeded by initial MeNC adduct formation followed by an isomerization involving the migratory insertion of the MeNC carbon into the Ge-C ligand bond. Addition of excess MeNC led to sequential insertions of two further MeNC molecules into the Ge-C bond. The insertion of the third MeNC leads to methylisocyanide methyl group C-H activation to afford an azagermacyclopentadienyl species. The X-ray crystal structures of the 1:1 (Ar(Me6))2GeCNMe adduct, the first and final insertion products (Ar(Me6))GeC(NMe)Ar(Me6) and (Ar(Me6))GeC(NHMe)C(NMe)C(Ar(Me6))NMe were obtained. The DFT calculations on the reaction pathways represent the first detailed mechanistic study of isocyanide oligomerization by a p-block element species.
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: Jeremy D
authors.initials: JD
authors.lastname: Erickson
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