A series of molybdenum pincer complexes has been shown for the first time to be active in the catalytic hydrogenation of amides.

Dedicated to Prof. Dr. Uwe Rosenthal on the occasion of his 70 th birthday A series of molybdenum(0), (I) and (II) complexes ligated by different PNP and NNN pincer ligands were synthesized and structurally characterized. Along with previously described MoÀ PNP complexes Mo-1 and Mo-2, all prepared compounds were tested in the catalytic hydrogenation of aromatic nitriles to primary amines. Among the applied catalysts, Mo-1 is particularly well suited for the hydrogenation of electron-rich benzonitriles. Additionally, two aliphatic nitriles were transformed into the desired products in 80 and 86 %, respectively. Moreover, catalytic intermediate Mo-1a was isolated and its role in the catalytic cycle was subsequently demonstrated.

A straightforward methodology for the synthesis of anti‐Markovnikov‐type alcohols is presented. By using a specific cobalt triphos complex in the presence of Zn(OTf) 2 as an additive, the hydrogenation of epoxides proceeds with high yields and selectivities. The described protocol shows a broad substrate scope, including multi‐substituted internal and terminal epoxides, as well as a good functional‐group tolerance. Various natural‐product derivatives, including steroids, terpenoids, and sesquiterpenoids, gave access to the corresponding alcohols in moderate‐to‐excellent yields.

A family of low-valent molybdenum complexes, supported by the pincer ligand ( i Pr 2 PCH 2 CH 2 ) 2 NH, was prepared and characterized. After activation by NaBHEt 3 coordination compounds 2 and 3-Cl were found to be suitable catalysts for the hydrogenation of ketones and olefins. Article pubs.acs.org/Organometallics