A coordination compound of Ge(0) stabilized by a diiminopyridine ligand

Terry Chu; Lee Belding; Art van der Est; Travis Dudding; Ilia Korobkov; Georgii I Nikonov

doi:10.1002/anie.201309421

A coordination compound of Ge(0) stabilized by a diiminopyridine ligand

Angew Chem Int Ed Engl. 2014 Mar 3;53(10):2711-5. doi: 10.1002/anie.201309421. Epub 2014 Feb 2.

Authors

Terry Chu¹, Lee Belding, Art van der Est, Travis Dudding, Ilia Korobkov, Georgii I Nikonov

Affiliation

¹ Chemistry Department, Brock University, 500 Glenridge Ave., St. Catharines, ON, L2S 3A1 (Canada).

PMID: 24488623
DOI: 10.1002/anie.201309421

Abstract

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.

Keywords: DFT calculations; EPR spectroscopy; germanium; low oxidation states; pyridine.