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Selective Lanthanide-catalysed Reactions. Catalytic Properties of Sm and Yb Metal Vapour Deposition Products

DOI: 10.1039/f19898501647

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Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1647 - 1654 (1989)

Update date:2022-08-11

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Authors:

Imamura, HayaoImamura, Hayao

Kitajima, KeijiKitajima, Keiji

Tsuchiya, SusumuTsuchiya, Susumu

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Article abstract of DOI:10.1039/f19898501647

The characteristics of lanthanide catalysts obtained when Sm and Yb were vaporized into a frozen organic (tetrahydrofuran, benzene and methylcyclohexane) matrix (77 K) were investigated.These low-valent, highly dispersed lanthanide particles (indicated as Sm/THF, Sm/benzene, Yb/THF, Yb/benzene etc.) were catalytically active and selective for hydrogenation and isomerization.Samarium usually showed a greater activity than ytterbium.Olefin hydrogenation obeyed the rate law v=kPH, suggesting that the reaction is controlled by catalytic activation of hydrogen.The molecular isotopic identity of hydrogen was conserved during the hydrogenation.Yb/THF and Yb/benzene were active for partial hydrogenation of benzene to cyclohexene.For the hydrogenation of olefins and acetylenes the substrate specificity was high; thus C-C double bonds were more readily reduced than triple bonds.The samarium and ytterbium catalysts discriminate between terminal and internal C-C triple bonds, only internal C<*>C bonds (but-2-yne and pent-2-yne) being reduced very selectively in contrast to acetylene, methylacetylene and but-1-yne.Solid base character of the lanthanide provides a cause for these differences in catalytic properties.

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