0000000000310311
AUTHOR
Zachary D. Brown
Mechanistic Study of Stepwise Methylisocyanide Coupling and C-H Activation Mediated by a Low-Valent Main Group Molecule
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 …
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
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.
CCDC 954558: Experimental Crystal Structure Determination
Related Article: Zachary D. Brown , Petra Vasko , Jeremy D. Erickson , James C. Fettinger , Heikki M. Tuononen , and Philip P. Power|2013|J.Am.Chem.Soc.|135|6257|doi:10.1021/ja4003553
CCDC 954559: Experimental Crystal Structure Determination
Related Article: Zachary D. Brown , Petra Vasko , Jeremy D. Erickson , James C. Fettinger , Heikki M. Tuononen , and Philip P. Power|2013|J.Am.Chem.Soc.|135|6257|doi:10.1021/ja4003553
CCDC 954557: Experimental Crystal Structure Determination
Related Article: Zachary D. Brown , Petra Vasko , Jeremy D. Erickson , James C. Fettinger , Heikki M. Tuononen , and Philip P. Power|2013|J.Am.Chem.Soc.|135|6257|doi:10.1021/ja4003553