The preparation and properties of tris(triphenylphosphine)halogenorhodium(I) and some reactions thereof including catalytic homogeneous hydrogenation of olefins and acetylenes and their derivatives

Abstract

Tris(triphenylphosphine)chlororhodium(I), RhCl(PPh₃)₃, has been prepared by the interaction of an excess of triphenylphosphine with rhodium(III) chloride hydrate in ethanol; the corresponding bromide and iodide are also described. The dissociation of the complex in various solvents has been investigated, and its reactions with hydrogen, ethylene, and carbon monoxide and aldehydes studied. Dihydrido- and ethylene complexes have been isolated and studied by nuclear magnetic resonance (n.m.r.) spectroscopy. Approximate values for the formation constants of ethylene and propylene complexes have been obtained; the latter is lower by a factor of over 10³. By electron spin resonance spectroscopy, the complex RhCl(PPh₃)₃ has been shown to contain trace amounts of a paramagnetic species, probably a rhodium(II) complex.

In homogeneous solution the tris(triphenylphosphine) complexes are exceedingly active catalysts for the rapid and homogeneous hydrogenation, at ca. 1 atmosphere of hydrogen pressure and room temperature, of unsaturated compounds containing isolated olefinic and acetylenic linkages.

The rates of hydrogenation of hept-1-ene, cyclohexene and hex-1-yne have been studied quantitatively and the dependence on factors such as substrate and catalyst concentration, temperature, and pressure determined. The data can be accommodated by a rate expression of the form: Rate =K_p[S][A]//_{1 +K1p+K2[S]} where [S] and [A] are the olefin and catalyst concentrations, respectively, and p is the concentration of hydrogen in solution.

From the data for cyclohexene the activation energy for the rate determining step is E_a= 22·9 kcal. mole^–1(ΔH‡= 22·3 kcal. mole^–1) and the value of ΔS‡= 12·9 e.u.

It is shown that the rate of hydrogen–deuterium exchange under selected conditions is quite slow compared with the rates of hydrogenation of olefins and, furthermore, that when H₂–D₂ mixtures are used in the reactions, alkanes and dideuteroalkanes are the major products. Reductions of maleic and fumaric acids with deuterium shows that cis-addition occurs preferentially. Similarly, in the reduction of hex-2-yne to n-hexane, cis-hex-2-ene is found to be the major olefin intermediate.

A mechanism for the hydrogenation is proposed in which the metal complex serves as a template to which a hydrogen molecule and an olefin molecule are briefly co-ordinated before transfer of one to the other takes place. The low kinetic isotope effect (rate H₂/rate D₂= 0·9) suggests that synchronous breaking of Rh–H bonds and making of C–H bonds takes place in the transition state involving two simultaneous three-centre interactions.