Kalikhman, InnaInnaKalikhmanKertsnus-Banchik, EvgeniaEvgeniaKertsnus-BanchikGostevskii, BorisBorisGostevskiiKocher, NikolausNikolausKocherStalke, DietmarDietmarStalkeKost, DanielDanielKost2018-11-072018-11-072009https://resolver.sub.uni-goettingen.de/purl?gro-2/17579Hexacoordinate silicon dichelates with hydrido and methyl monodentate ligands were prepared by transsilylation. The temperature-dependent (29)Si NMR spectra of toluene-d(8) or CDCl(3) solutions provide evidence for a reversible, neutral dissociation of the dative N-Si bond, accompanied by a shift of the (29)Si resonance from high field (hexacoordinate) to lower field (pentacoordinate) with increasing temperature. When a phenyl group is attached directly to silicon (replacing methyl), the N-Si dissociation is prevented, presumably due to electron withdrawal by the phenyl. Two of the silicon complexes were characterized by crystallographic analysis. Quantum chemical calculations at the RB3LYP/6-31G(d) level confirm the stability of an N-Si dissociated species (1.03 kcal mol(-1) lower in energy than the hexacoordinate dichelate) and rule out the alternative possibility of an O-Si zwitterionic dissociation, thus supporting the mechanism suggested by the experimental results.journal_article10.1021/om8008487000262608600019