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Exploiting Electrostatics To Generate Unsaturation: Oxidative GeE Bond Formation Using a Non π‐Donor Stabilized [R(L)Ge:] + Cation
Author(s) -
Rit Arnab,
Tirfoin Rémi,
Aldridge Simon
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508940
Subject(s) - degree of unsaturation , chemistry , germanium , steric effects , oxidative addition , metal , electrostatics , center (category theory) , crystallography , stereochemistry , photochemistry , polymer chemistry , organic chemistry , catalysis , silicon
The two‐coordinate germanium cation [(IDipp){(Me 3 Si) 2 CH}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 ME 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.