Geometrically Constrained Cationic Low-Coordinate Tetrylenes: Highly Lewis Acidic σ-Donor Ligands in Catalytic Systems.

A novel non-innocent ligand class, namely cationic single-centre ambiphiles, is reported in the phosphine-functionalised cationic tetrylene Ni0 complexes, [PhR DippENi(PPh3 )3 ]+ (4 a/b (Ge) and 5 (Sn); PhR Dipp={[Ph2 PCH2 SiR2 ](Dipp)N}- ; R=Ph, i Pr; Dipp=2,6-i Pr2 C6 H3 ). The inherent electronic nature of low-coordinate tetryliumylidenes, combined with the geometrically constrained [N-E-Ni] bending angle enforced by the chelating phosphine arm in these complexes, leads to strongly electrophilic EII centres which readily bind nucleophiles, reversibly in the case of NH3 . Further, the GeII centre in 4 a/b readily abstracts the fluoride ion from [SbF6 ]- to form the fluoro-germylene complex PhR DippGe(F)Ni(PPh3 )3 9, despite this GeII centre simultaneously being a σ-donating ligand towards Ni0 . Alongside the observed catalytic ability of 4 and 5 in the hydrosilylation of alkynes and alkenes, this forms an exciting introduction to a multi-talented ligand class in cationic single-centre ambiphiles.