화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.136, No.32, 11300-11303, 2014
Synthesis and Unexpected Reactivity of Germyliumylidene Hydride [:GeH](+) Stabilized by a Bis(N-heterocyclic carbene)borate Ligand
Employing the potassium salt of the monoanionic bis(NHC)borate 1 (NHC = N-Heterocyclic Carbene) enables the synthesis and isolation of the bis(NHC)borate-stabilized chlorogermyliumylidene pre-cursor 2 in 61% yield. A Cl/H exchange reaction of 2 using potassium trisec.-butylborhydride as a hydride source leads to the isolation of the first germyliumylidene hydride [HGe:(+)] complex 3 in 91% yield. The Ge(II)-H bond in the latter compound has an unexpected reactivity as shown by the reaction with the potential hydride scavenger [Ph3C][B(C6F5)(4)], furnishing the corresponding HGe: -> CPh3 cation in the ion pair 4 as initial product. Compound 4 liberates HCPh3 in the presence of 3 to give the unusual dinuclear HGe -> Ge: cation in 5. The latter represents the first three-coordinate dicationic Ge(II) species stabilized by an anionic bis(NHC) chelate ligand and a Ge(II) donor. All novel compounds were fully characterized, including X-ray diffraction analyses.