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. 2018 Nov 13;10(4):1150-1157.
doi: 10.1039/c8sc03969k. eCollection 2019 Jan 28.

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

Simone V Samuelsen  1 , Carola Santilli  1 , Mårten S G Ahlquist  2 , Robert Madsen  1
Affiliations

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

Simone V Samuelsen et al. Chem Sci. .

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.

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Figures

Fig. 1
Fig. 1. Manganese(i) complexes for alcohol dehydrogenation.,
Fig. 2
Fig. 2. Manganese(iii) salen/salan complexes used in the investigation.
Scheme 1
Scheme 1. Pyrrole synthesis from but-2-ene-1,4-diol and amines.
Fig. 3
Fig. 3. Hammett plot for the imination with para-substituted benzyl alcohols.
Fig. 4
Fig. 4. Activation of Mn(iii)(salen)OBn to form the active amido complex.
Fig. 5
Fig. 5. Proposed catalytic cycle and relative Gibbs free energies.
Fig. 6
Fig. 6. Hammett plot calculated by DFT.
See this image and copyright information in PMC

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