First Insertions of Carbene Ligands into Ge-N and Si-N Bonds

Lucía Álvarez-Rodríguez; Javier A Cabeza; Pablo García-Álvarez; Mar Gómez-Gallego; Alba D Merinero; Miguel A Sierra

doi:10.1002/chem.201700828

First Insertions of Carbene Ligands into Ge-N and Si-N Bonds

Chemistry. 2017 Mar 28;23(18):4287-4291. doi: 10.1002/chem.201700828. Epub 2017 Mar 15.

Authors

Lucía Álvarez-Rodríguez^{1

2}, Javier A Cabeza^{1

2}, Pablo García-Álvarez^{1

2}, Mar Gómez-Gallego^{1

3}, Alba D Merinero^{1

3}, Miguel A Sierra^{1

3}

Affiliations

¹ Centro de Innovación en Química Avanzada (ORFEO-CINQA), Spain.
² Departamento de Química Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo-CSIC, 33071, Oviedo, Spain.
³ Departamento de Química Orgánica, Universidad Complutense, 28040, Madrid, Spain.

PMID: 28225557
DOI: 10.1002/chem.201700828

Abstract

The insertion of carbene ligands into Ge-N (three examples) and Si-N (one example) bonds has been achieved for the first time by treating Fischer carbene complexes (M=W, Cr) with bulky amidinatotetrylenes (E=Ge, Si). These reactions, which start with a nucleophilic attack of the amidinatotetrylene heavier group 14 atom to the carbene C atom, proceed through a stereoselective insertion of the carbene fragment into an E-N bond of the amidinatotetrylene ENCN four-membered ring, leading to [M(CO)₅ L] derivatives in which L belongs to a novel family of tetrylene ligands comprising an ECNCN five-membered ring.

Keywords: Fischer carbenes; carbene insertion; germanium; silicon; tetrylenes.