Molecular Defined Molybdenum–Pincer Complexes and Their Application in Catalytic Hydrogenations

Abstract

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

Synthesis of Molybdenum Pincer Complexes and Their Application in the Catalytic Hydrogenation of Nitriles

“…However, no hydride signals could be detected according to the obtained 1 H NMR spectrum. The resonance at 75.9 ppm corresponds to the Mo(0) complex fac ‐[( i Pr 2 PCH 2 CH 2 ) 2 NH]Mo(CO) 3 , revealing a potential catalyst deactivation pathway.…”

Highly selective hydrogenation of amides catalysed by a molybdenum pincer complex: scope and mechanism

“…Among the described complexes, Mo-1a (Table 1) was shown to be active in the catalytic hydrogenation of different acetophenones and styrenes. 18 Similar Mo-systems have also been used for the hydrogenation of CO 2 , imines and nitriles. 19 Based on these reports and our previous work, we became interested in the behaviour of such base-metal catalysts for the reductive cleavage of amides.…”

Molecularly Defined Manganese Catalyst for Low-Temperature Hydrogenation of Carbon Monoxide to Methanol

“…A breakthrough in this field occurred in 2010 when Milstein and co-workers presented a highly selective catalytic hydrogenolysis to corresponding amines and alcohols, promoted by ruthenium complexes. 24 Since then, a number of other systems based on Ru, 25−33 Fe, 34−37 Ag, 38 Mo, 39 and Mn 40 for amide C−N hydrogenation have been suggested. 41 In addition, hydrogenation of formamides has created significant attention in the context of carbon dioxide reduction.…”

“…A breakthrough in this field occurred in 2010 when Milstein and co-workers presented a highly selective catalytic hydrogenolysis to corresponding amines and alcohols, promoted by ruthenium complexes . Since then, a number of other systems based on Ru, − Fe, − Ag, Mo, and Mn for amide C–N hydrogenation have been suggested . In addition, hydrogenation of formamides has created significant attention in the context of carbon dioxide reduction. − Notably, Prakash and co-workers reported a dramatic drop in activity for formamide hydrogenation in the presence of even trace amounts of CO, indicating the serious challenge of CO-to-methanol hydrogenation (Figure B).…”