From Diaminosilylenes to Silapyramidanes: Making Sense of the Stability of Divalent Silicon Compounds.

ABSTRACT: Since the discovery of decamethylsilicocene over three decades ago, chemists have successfully isolated a variety of divalent silicon compounds by orchestrating steric and electronic effects to their advantage. Two broad strategies of electronic stabilization appear to have been widely deployed, namely, π-conjugation as in diaminosilylenes and π-complexation as in decamethylsilicocene and silapyramidanes. Herein, we attempted to identify quantitative metrics for the electronic stabilization of silylenes. Singlet-triplet gaps and electron affinities, both physical observables, proved useful in this regard. Thus, the most stable silylenes exhibit unusually large singlet-triplet gaps and very low or negative gas-phase electron affinities. Both metrics signify low electrophilicity, i.e., a low

SUBMITTER: Torstensen K 

PROVIDER: S-EPMC10853992 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature