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

Authors
  • Weber, Stefan1
  • Veiros, Luis F2
  • Kirchner, Karl1
  • 1 Institute of Applied Synthetic Chemistry Vienna University of Technology Getreidemarkt 9/163-AC A-1060 Wien Austria. , (Austria)
  • 2 Centro de Química Estrutural, Instituto Superior Técnico Universidade de Lisboa Av. Rovisco Pais No. 1 1049-001 Lisboa Portugal. , (Portugal)
Type
Published Article
Journal
Advanced Synthesis & Catalysis
Publisher
Wiley
Publication Date
Dec 03, 2019
Volume
361
Issue
23
Pages
5412–5420
Identifiers
DOI: 10.1002/adsc.201901040
PMID: 31875866
Source
Medline
Keywords
Language
English
License
Unknown

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. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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