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Old Concepts, New Application - Additive-Free Hydrogenation of Nitriles Catalyzed by an Air Stable Alkyl Mn(I) Complex.

ABSTRACT: An efficient additive-free manganese-catalyzed hydrogenation of nitriles to primary amines with molecular hydrogen is described. The pre-catalyst, a well-defined bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dpre)(CO)₃(CH₃)] (dpre=1,2-bis(di-n-propylphosphino)ethane), undergoes CO migratory insertion into the manganese-alkyl bond to form acyl complexes which upon hydrogenolysis yields the active coordinatively unsaturated Mn(I) hydride catalyst [Mn(dpre)(CO)₂(H)]. A range of aromatic and aliphatic nitriles were efficiently and selectively converted into primary amines in good to excellent yields. The hydrogenation of nitriles proceeds at 100?°C with a catalyst loading of 2?mol?% and a hydrogen pressure of 50?bar. Mechanistic insights are provided by means of DFT calculations.

SUBMITTER: Weber S

PROVIDER: S-EPMC6916632 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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Old Concepts, New Application - Additive-Free Hydrogenation of Nitriles Catalyzed by an Air Stable Alkyl Mn(I) Complex.

Weber Stefan S Veiros Luis F LF Kirchner Karl K

Advanced synthesis & catalysis 20191028 23

An efficient additive-free manganese-catalyzed hydrogenation of nitriles to primary amines with molecular hydrogen is described. The pre-catalyst, a well-defined bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dpre)(CO)3(CH3)] (dpre=1,2-bis(di-n-propylphosphino)ethane), undergoes CO migratory insertion into the manganese-alkyl bond to form acyl complexes which upon hydrogenolysis yields the active coordinatively unsaturated Mn(I) hydride catalyst [Mn(dpr ...[more]

PMID: 31875866

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