Exploiting Electrostatics To Generate Unsaturation: Oxidative Ge=E Bond Formation Using a Non π-Donor Stabilized [R(L)Ge:](+) Cation

Arnab Rit; Rémi Tirfoin; Simon Aldridge

doi:10.1002/anie.201508940

Exploiting Electrostatics To Generate Unsaturation: Oxidative Ge=E Bond Formation Using a Non π-Donor Stabilized [R(L)Ge:](+) Cation

Angew Chem Int Ed Engl. 2016 Jan 4;55(1):378-82. doi: 10.1002/anie.201508940. Epub 2015 Nov 6.

Authors

Arnab Rit¹, Rémi Tirfoin², Simon Aldridge³

Affiliations

¹ Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK). arnab.rit@chem.ox.ac.uk.
² Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK).
³ Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK). simon.aldridge@chem.ox.ac.uk.

PMID: 26545498
DOI: 10.1002/anie.201508940

Abstract

The two-coordinate germanium cation [(IDipp){(Me3Si)2CH}Ge:](+) has been synthesized, which lacks π-donor stabilization of the metal center and consequently has a very small HOMO-LUMO gap (187 kJ mol(-1)). It undergoes a variety of facile oxidative bond-forming reactions, most notably allowing access to the first examples of Group 14 metal cations containing M=E multiple bonds (E = C, N). The use of an electrostatic (rather than purely steric) strategy to discourage aggregation means that less bulky systems (for example, containing a primary alkylidene fragment, =CHR) are accessible.

Keywords: N-heterocyclic carbenes; bond activation; germanium; main group elements; multiple bonds.

Publication types

Research Support, Non-U.S. Gov't