Synthesis and redox catalysis of Carbodiphosphorane ligated stannylene

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 14, 2024

Heavier group 14 carbene analogues, exhibiting transition-metal-like behavior, display remarkable capability for small molecule activation and coordination chemistry. However, their application in redox catalysis remains elusive. In this paper, we report the synthesis isolation of a stannylene with carbodiphosphorane ligand. The nucleophilic reactivity at divalent tin center is elucidated by computational studies. Moreover, exhibits catalytic activity hydrodefluorination reaction fluoroarenes. Mechanistic investigations into elementary steps confirm Sn

Язык: Английский

Dicationic 1-Germa and 1-Stannavinylidenes: Synthesis, Structure, and Reactivity

JACS Au, Год журнала: 2025, Номер 5(3), С. 1289 - 1298

Опубликована: Фев. 19, 2025

The synthesis of heteronuclear vinylidene analogues containing heavier group 14 elements (R2C═E:, E = Si, Ge, Sn) has been a challenging task due to their inherent instability. In this study, we report the dicationic 1-germavinylidene (3Ge) and 1-stannavinylidene (3Sn) by using sym-bis(2-pyridyl)-tetraphenylcarbodiphosphorane (CDPPy2) as donor ligand. Both 3Ge 3Sn have characterized single-crystal X-ray diffraction analysis, NMR spectroscopy, high-resolution mass spectrometry. structural supported results theoretical calculations, confirms that feature polarized C═E double bond lone pair electrons located at atom (E Ge Sn). reactions with IDippMCl (M Cu, Ag, Au) give M–Cl addition products. Mechanistic studies on activation Au–Cl demonstrate its ambiphilicity. This work represents an example utilization carbone ligand both σ π for analogues.

Язык: Английский