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. 2016 Aug 22;22(35):12316-20.
doi: 10.1002/chem.201603148. Epub 2016 Jul 27.

Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride Mn(I) and Fe(II) PNP Pincer Complexes

Matthias Mastalir  1 , Mathias Glatz  1 , Nikolaus Gorgas  1 , Berthold Stöger  2 , Ernst Pittenauer  2 , Günter Allmaier  2 , Luis F Veiros  3 , Karl Kirchner  4
Affiliations

Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride Mn(I) and Fe(II) PNP Pincer Complexes

Matthias Mastalir et al. Chemistry. .

Abstract

Herein, we describe an efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride Mn(I) and Fe(II) complexes, which are stabilized by a PNP ligand based on the 2,6-diaminopyridine scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant non-precious metal catalysts, and is based on the acceptorless alcohol dehydrogenation concept. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted in good to excellent isolated yields. Although in the case of Mn selectively imines were obtained, with Fe-exclusively monoalkylated amines were formed. These reactions proceed under base-free conditions and required the addition of molecular sieves.

Keywords: alcohols; amination; homogeneous catalysis; iron; manganese.

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