Development and mechanistic investigation of the manganese(iii) salen-catalyzed dehydrogenation of alcohols

Simone V. Samuelsen, Carola Santilli, Mårten S.G. Ahlquist, Robert Madsen*

*Corresponding author for this work

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Abstract

The first example of a manganese(iii) catalyst for the acceptorless dehydrogenation of alcohols is presented. N,N′-Bis(salicylidene)-1,2-cyclohexanediaminomanganese(iii) chloride (2) has been shown to catalyze the direct synthesis of imines from a variety of alcohols and amines with the liberation of hydrogen gas. The mechanism has been investigated experimentally with labelled substrates and theoretically with DFT calculations. The results indicate a metal-ligand bifunctional pathway in which both imine groups in the salen ligand are first reduced to form a manganese(iii) amido complex as the catalytically active species. Dehydrogenation of the alcohol then takes place by a stepwise outer-sphere hydrogen transfer generating a manganese(iii) salan hydride from which hydrogen gas is released.

Original languageEnglish
JournalChemical Science
Volume10
Issue number4
Pages (from-to)1150-1157
Number of pages8
ISSN2041-6520
DOIs
Publication statusPublished - 2019

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