An NHC‐Stabilized H(2)GeBH(2) Precursor for the Preparation of Cationic Group 13/14/15 Hydride Chains

The synthesis, characterization and reactivity studies of the NHC‐stabilized complex IDipp ⋅ GeH(2)BH(2)OTf (1) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) are reported. Nucleophilic substitution of the triflate (OTf) group in 1 by phosphine or arsine donors provides access to the cationic group 13/14/15 chains [IDipp ⋅ GeH(2)BH(2)ERR(1)R(2)](+) (2 E=P; R, R(1)=H; R(2)=(t)Bu; 3 E=P; R=H; R(1), R(2)=Ph; 4 a E=P; R, R(1), R(2)=Ph; 4 b E=As; R, R(1), R(2)=Ph). These novel cationic chains were characterized by X‐ray crystallography, NMR spectroscopy and mass spectrometry. Moreover, the formation of the parent complexes [IDipp ⋅ GeH(2)BH(2)PH(3)][OTf] (5) and [IDipp ⋅ GeH(3)][OTf] (6) were achieved by reaction of 1 with PH(3). Accompanying DFT computations give insight into the stability of the formed chains with respect to their decomposition.