Published: May 13, 2024

Transition metal-catalyzed alkene isomerization is an enabling technology used to install distal its original site. Due their well-defined structure, homogeneous catalysts can be fine-tuned optimize reactivity, stereoselectivity, and positional selectivity, but they often suffer from instability non-recyclability. Heterogeneous are generally highly robust continue lack active-site specificity challenging rationally improve through structural modification. Known single-site heterogeneous for utilize precious metals bespoke, expensive, synthetically intense supports. Additionally, have mediocre inspiring us develop a catalyst with active site made readily available compounds of Earth-abundant elements. Previous work demonstrated that very formed upon protonation Ni[P(OEt)3]4 by H2SO4, generating [Ni–H]+ This incredibly active, also decomposes readily, which severely limits utility. Herein we show using solid acid (sulfated zirconia, SZO300), not only this de-composition prevented, high activity maintained, improved selectivity achieved, broader scope functional groups tolerated. Preliminary mechanistic experiments suggest the catalytic reaction likely goes intermolecular, two-electron pathway. A detailed kinetic study comparing state-of-the-art Ni Pd reveals highest seen Ni/SZO300 system. The reactivity Ni/SZO300, limited isomerization; it competent hydroalkenylation, hydroboration, hydrosilylation, demonstrating broad application catalyst.

Language: Английский