Journal article
Development and mechanistic investigation of the manganese(iii) salen-catalyzed dehydrogenation of alcohols
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.
Language: | English |
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Publisher: | Royal Society of Chemistry |
Year: | 2019 |
Pages: | 1150-1157 |
ISSN: | 20416539 and 20416520 |
Types: | Journal article |
DOI: | 10.1039/c8sc03969k |
ORCIDs: | Samuelsen, Simone V. and Madsen, Robert |