Interrogating the anti-Insertion of Alkynes into Gold(III)

JACS Au, Год журнала: 2025, Номер 5(3), С. 1439 - 1447

Опубликована: Фев. 26, 2025

Alkyne hydrofunctionalizations are a powerful strategy to efficiently build up structural complexity. The selectivity of these reactions is typically governed by the interaction between alkyne and metal-hydride, which commonly proceeds via well-understood syn-insertion mechanism. In contrast, anti-insertions far less common, with proposed mechanisms often extrapolated from literature precedents rather than grounded in direct experimental evidence. While gold complexes rank among most efficient catalysts for such transformations, mechanistic understanding key insertion step remains incomplete. this study, we demonstrate that stable gold(III)-hydrides, featuring (P∧N∧C) ligand, undergo selective alkynes yield corresponding anti-Markovnikov Z-vinyl complexes. A combination control experiments, kinetic studies, computational analyses reveals nonradical, bimolecular process, water plays pivotal role accelerating reaction potentially stabilizing highly reactive, T-shaped gold(I) intermediate. Notably, first demonstration both activated unactivated terminal internal into gold(III)-hydride complex.

Язык: Английский

Artificial Mimicking Hydrogen-Stored Process in Natural Photosynthesis for Improved CO2 Reduction

Applied Catalysis B Environment and Energy, Год журнала: 2025, Номер 377, С. 125508 - 125508

Опубликована: Май 19, 2025

Язык: Английский

Exploring Spin‐Orbit Effects in a [Cu₆Tl]⁺ Nanocluster Featuring an Uncommon Tl−H Interaction

Chemistry - A European Journal, Год журнала: 2024, Номер 30(25)

Опубликована: Фев. 21, 2024

Reaction of [CuH(PPh

Язык: Английский