0000000000907355
AUTHOR
Zachary Brown
showing 2 related works from this author
A Germanium Isocyanide Complex Featuring (n → π*) Back-Bonding and Its Conversion to a Hydride/Cyanide Product via C-H Bond Activation under Mild Con…
2012
Reaction of the diarylgermylene Ge(ArMe6)2 [ArMe6 = C6H3-2,6-(C6H2-2,4,6-(CH3)3)2] with tert-butyl isocyanide gave the Lewis adduct species (ArMe6)2GeCNBut, 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–But bond. peerReviewed
Mechanistic Study of Stepwise Methylisocyanide Coupling and C-H Activation Mediated by a Low-Valent Main Group Molecule
2013
An experimental and DFT investigation of the mechanism of the coupling of methylisocyanide and C–H activation mediated by the germylene (germanediyl) Ge(ArMe6)2 (ArMe6 = 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 (ArMe6)2GeCNMe adduct, the first and final insertion produc…