Isolation and Reactivity of Chlorotetryliumylidenes Using a Bidentate Bis(N-heterocyclic imine) Ligand

Florian S. Tschernuth, Franziska Hanusch, Tibor Szilvási, Shigeyoshi Inoue

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20 Scopus citations

Abstract

By use of the ethylene-bridged bidentate bis-NHI (NHI = N-heterocyclic imine) ligand 1 toward the complexation of ECl2·(dioxane) (E = Ge, Sn) the synthesis of the first bis-NHI-stabilized chlorogermyliumylidene 2a[GeCl3] and chlorostannyliumylidene 2b[SnCl3] by Lewis base mediated autoionization was achieved. Using additional TMSOTf enabled the isolation of the corresponding triflate salts 2a[OTf] and 2b[OTf] in moderate yields. The obtained tetryliumylidene ions were fully characterized, including single-crystal X-ray diffraction analysis, and additionally investigated by density functional theory calculations. Reaction of 2a[OTf] with NaBH4led to the formation of a push-pull-stabilized hydridogermyliumylidene complex by Cl/H exchange. The same reaction with the stannyliumylidene led to transmetalation, yielding the corresponding dihydroboronium complex. Also, reactions with LiAlH4in both cases afforded the transmetalation product.

Original languageEnglish
Pages (from-to)4265-4272
Number of pages8
JournalOrganometallics
Volume39
Issue number23
DOIs
StatePublished - 14 Dec 2020

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