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

摘要

The two-coordinate germanium cation (IDipp)-{( Me3Si)(2)CH}GeD(+) has been synthesized, which lacks p-donor stabilization of the metal center and consequently has a very small HOMO-LUMO gap (187 kJmol(-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.