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

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 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.