Small Molecule Activation by 4‐N,N‐Dimethylaminopyridine‐Stabilized Bis(silyl)germylenes

The synthesis, characterization, and reactivity of DMAP⋅Ge(Si t Bu 3 )Si(TMS) 3 1 a and DMAP⋅Ge[Si(TMS) 3 ] 2 1 b are reported (DMAP = 4‐ N,N ‐Dimethylaminopyridine). These germylenes were isolated in moderate yields by the reaction of DMAP⋅GeCl 2 with NaSi t Bu 3 ⋅(THF) 2 and KSi(TMS) 3 ⋅(THF) 1.2 or 2 equivalents of KSi(TMS) 3 ⋅(THF) 1.2 , respectively, at low temperature (TMS = Trimethylsilyl). Exposure of 1 a to dihydrogen forms the tetravalent germanium hydride species GeH 2 (Si t Bu 3 )Si(TMS) 3 2 a . Additionally, the reactivity of 1 a,b towards the substitution of 2,6‐dimethylphenyl isocyanide (CNXyl) 3 a , b , the alkyne cycloaddition of diphenylacetylene (PhCCPh) 4 a , b , and the substitution of DMAP for NHC using 1,3,4,5‐tetramethylimidazol‐2‐ylidene (IMe 4 ) 5 a , b was investigated (NHC = N ‐heterocyclic carbene). Reaction products were characterized by multinuclear magnetic resonance (NMR), infrared (IR) spectroscopy, mass spectrometric analysis, and single‐crystal X‐ray diffraction (SC‐XRD) study.