A Coordination Compound of Ge~0 Stabilized by a Diiminopyridine Ligand

摘要

Reduction of the cationic Ge~(II) complex [dimpyrGeCl][GeCl3] (dimpyr=2,6-(ArN = CMe)2NC5H3: Ar=2,6-iPr2C6H3) with potassium graphite in benzene affords an air sensitive, dark green compound of Ge~0, [dimpyrGe], which is stabilized by a bis(imino)pyridine platform. This compound is the first example of a complex of a zero-valent Group 14 element that does not contain a carbene or carbenoid ligand. This species has a singlet ground state. DFT studies revealed partial delocalization of one of the Ge lone pairs over the π*(C=N) orbitals of the imines. This delocalization results in a partial multiple-bond character between the Ge atom and imine nitrogen atoms, a fact supported by the X-ray crystallography and IR spectroscopy data.