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Catalytic Activity of Polynuclear Platinum Carbonyl Anions in Homogeneous Hydrogenation Reactions

DOI: 10.1039/DT9820000727

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 727 - 732 (1982)

Update date:2022-08-11

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Authors:

Bhaduri, SumitBhaduri, Sumit

Sharma, Krishna R.Sharma, Krishna R.

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Article abstract of DOI:10.1039/DT9820000727

The homogeneous hydrogenation of benzaldehyde, heptanal, cyclohexanone, cyclohexene, acetonitrile, and benzonitrile has been studied using n4>2<(Pt3(CO)6)5> (1) as the catalyst over a range of temperature (40-80 deg C) and pressure (20-64 lbf in-2).Infrared spectroscopic studies suggest the formation of a common intermediate in reactions carried out at >=60 deg C.Benzaldehyde is the most readily hydrogenated; the nature of the products depends on the pressure of hydrogen used and is selective to either benzyl alcohol or a mixture of benzene and methanol.Kinetic studies on the rate of benzyl alcohol formation indicate a first-order dependence of the rate on the concentration of (1).While the rate shows a Michaelis-Menten type of dependence on the PhCHO concentration, it seems to be independent of H2 pressure in the range 20-25 lbf in-2.Under these conditions, a value of 63.81 kJ mol-1 for the activation energy is obtained from the Arrhenius plot.A tentative mechanism for PhCHO hydrogenation is discussed.

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