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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...
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