Bis(N-Heterocyclic Carbene) Manganese(I) Complexes: Efficient and Simple Hydrogenation Catalysts.

The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. For that purpose, a series of complexes has been synthesized via an improved two step procedure utilizing bis(NHC)-BEt3 adducts. By applying complexes 3 with KHBEt3 as additive, various aromatic and aliphatic esters were hydrogenated successfully at mild temperatures and low catalyst loadings, highlighting the efficiency of the novel catalytic system. The versatility of the developed catalytic system was further demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes and alkenes. Mechanistic experiments and DFT calculations indicate an inner sphere mechanism with the loss of one CO ligand and reveal the role of BEt3 as cocatalyst.

Low-Valent Molybdenum PNP Pincer Complexes as Catalysts for the Semihydrogenation of Alkynes.

Low-valent molybdenum PNP pincer complexes were studied as catalysts for the semihydrogenation of alkynes. For that purpose, tBu-substituted PNP complexes PNP tBuMo(CO)2 (6a) and PNP tBuMo(CO)3 (6c) and the NNP complex NNP iPrMo(CO)2(PPh3) ((rac)-7) were synthesized and characterized. By utilizing the cyclohexyl-substituted complex PNPCyMo(CO)2(CH3CN) (5a), several diphenylacetylene derivatives are transformed to the corresponding (Z)-alkenes with good to very good diastereoselectivities (up to 91:9). Mechanistic experiments indicate an outer-sphere mechanism including metal-ligand cooperativity.