The Outstanding Ambiphilicity of Trialkylstibines among Trialkylpnictines: Power for Stepwise Deoxygenation and N–N Coupling of Nitroarenes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

The ongoing discovery of highly reactive ambiphilic main-group species has significantly advanced the development chemistry, particularly in realms small molecule activation and catalysis. Theoretically, compounds featuring smaller HOMO–LUMO gaps gain stronger ambiphilicity higher reactivity. In this work, we fundamentally demonstrate that Me3Sb holds smallest gap among trimethylpnictines, indicating its outstanding ambiphilicity. Correspondingly, superior reactivity toward deoxygenation electron-deficient nitroarenes been unambiguously revealed through control experiments. Furthermore, unprecedented SbIII/SbVO cycling between trialkylstibines their oxides established for catalytic transformation into azoxyarenes/azoarenes. This study opens a new chapter organoantimony derivatives fields redox

Language: Английский

Diphosphaenones: Beyond the Phosphorus Analogue of Enones

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

N-heterocyclic vinyl (NHV) substituted diphosphaenones 3a,b [R–PP–C(O)–R, RNHV] have been isolated and crystallographically characterized. They not only exhibit a planar trans PP–CO configuration, but also show conjugated 1,4-addition.

Language: Английский