Rhodium-Catalyzed Chemoselective Hydrosilylation of Nitriles to an Imine Oxidation Level Enabled by a Pincer-type Group 13 Metallylene Ligand

Syntheses and catalytic application of rhodium complexes having a pincer-type group 13 metallylene ligand are reported. The PGaIP–Rh complex exhibited high chemoselectivity for hydrosilylation of nitriles to an imine oxidation level, realizing efficient synthesis of oximes from nitriles with good functional group compatibility. A rhodium monohydride complex stabilized with PPh3 was synthesized and structurally characterized as a derivative of a plausible rhodium hydride intermediate.

本文报道了钳型第13族金属亚烯配体修饰的铑配合物的合成及其催化应用。所制备的PGaIP–Rh配合物对腈类的硅氢加成反应表现出优异的化学选择性，可将反应精准调控至亚胺氧化水平，实现了从腈类高效合成肟类化合物，且具有良好的官能团兼容性。此外，本研究合成了一种经三苯基膦（PPh3）稳定的一氢化铑配合物，并对其完成了结构表征，该配合物可作为合理推测的氢化铑反应中间体的衍生物。