低价钼PNP钳形配合物作为炔烃半氢化反应的催化剂

Both Niklas F, Spannenberg Anke, Junge Kathrin, Beller Matthias

Leibniz-Institut für Katalyse e.V., Albert-Einstein-Straße 29a, 18059 Rostock, Germany.

Organometallics. 2022 Jul 25;41(14):1797-1805. doi: 10.1021/acs.organomet.1c00709. Epub 2022 Mar 15.

Low-valent molybdenum PNP pincer complexes were studied as catalysts for the semihydrogenation of alkynes. For that purpose, Bu-substituted PNP complexes PNP Mo(CO) () and PNP Mo(CO) () and the NNP complex NNP Mo(CO)(PPh) (()-) were synthesized and characterized. By utilizing the cyclohexyl-substituted complex PNPMo(CO)(CHCN) (), several diphenylacetylene derivatives are transformed to the corresponding ()-alkenes with good to very good diastereoselectivities (up to 91:9). Mechanistic experiments indicate an outer-sphere mechanism including metal-ligand cooperativity.

低价钼PNP钳形配合物作为炔烃半氢化反应的催化剂进行了研究。为此，合成并表征了丁基取代的PNP配合物PNP Mo(CO)()和PNP Mo(CO)()以及NNP配合物NNP Mo(CO)(PPh) (() -)。通过使用环己基取代的配合物PNPMo(CO)(CHCN) ()，几种二苯乙炔衍生物以良好到非常好的非对映选择性（高达91:9）转化为相应的() -烯烃。机理实验表明这是一种包括金属-配体协同作用的外层机理。