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Studies on -Catalysed Homogeneous Transfer Hydrogenation Reactions; X-Ray Structure of

DOI: 10.1039/DT9900001305

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1305 - 1311 (1990)

Update date:2022-08-11

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Authors:

Bhaduri, SumitBhaduri, Sumit

Sapre, NiteenSapre, Niteen

Sharma, KrishnaSharma, Krishna

Jones, Peter G.Jones, Peter G.

Carpenter, GeneCarpenter, Gene

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Article abstract of DOI:10.1039/DT9900001305

Using (1) as the homogeneous precatalyst, transfer hydrogenations of cyclohex-2-en-1-one, benzylideneaniline, and carbon tetrahalides by donor alcohols, in particular propan-2-ol, have been studied.Conversion of cyclohex-2-en-1-one into cyclohexanol has been found to proceed via the intermediate formation of cyclohexanone.From the temperature dependence of the overall reaction rates, the precatalysts and are involved in processes with comparable activation energies.Two catalytically active cluster complexes, and , were isolated from the reaction of (1) with cyclohex-2-en-1-one.Hydrogenation of the tetranuclear cluster led to the formation of and .The reaction of the complex (1) with benzylideneaniline gave a catalytically active cluster .With (1) as the precatalyst, analogues of benzylideneaniline of general formula RC6H4CH=NPh can all be transfer hydrogenated, with the exception of the o-methoxy derivative.The complex was found to undergo reversible carbonylation.Rational syntheses for and were designed by treating (1) with the appropriate alcohol and carbon tetrahalide.The X-ray structure of has been determined.The halogenoalkoxo clusters are considered to be active intermediates in the overall catalytic cycle for the transfer hydrogenations of carbon tetrahalides.

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