钯
催化作用
替代(逻辑)
配体(生物化学)
氧化磷酸化
化学
氧化加成
取代反应
组合化学
药物化学
有机化学
受体
计算机科学
生物化学
程序设计语言
作者
Ian C. Chagunda,Antonia Kropp,David C. Leitch,J. Scott McIndoe
标识
DOI:10.26434/chemrxiv-2024-nx480
摘要
Palladium-catalyzed cross-coupling reactions are indispensable in chemical synthesis, but efficient in situ catalyst activation remains a persistent challenge. Current Pd(II) precatalysts often lead to inefficient catalyst activation, necessitating higher catalyst loadings and limiting selectivity. We investigated the ligand substitution and activation mechanism of the stable Pd(II) dialkyl complex (DMPDAB)Pd(CH2SiMe3)2 in real-time using mass spectrometric monitoring. The introduction of charged phosphine ligands enabled the detection of key catalytic intermediates and identification of off-cycle species. Our findings demonstrate a low activation energy for the ligand dissociation of the DMPDAB ligand and the reductive elimination of (Me3SiCH2)2 resulting in rapid formation of monoligated LPd(0) species, the active catalytic species for oxidative addition. These mechanistic insights offer a path towards developing more efficient and selective Pd-catalyzed processes, offering valuable guidance for the future design of precatalysts with improved performance.
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