Michael G. Burnett, Robert J. Morrison, Christopher J. Strugnell
1974
Citations
0
Influential Citations
5
Citations
Journal
Journal of The Chemical Society-dalton Transactions
Abstract
Buta-1,3-diene is catalytically hydrogenated to a mixture of butenes and butane by carbonylhydridotris(triphenylphosphine)iridium(I), IrH(CO)(PPh3)3, and by carbonyltrihydridobis(triphenylphosphine)iridium(III), IrH3(CO)(PPh3)2, at 50° in dimethylformamide. The rates observed could be predicted by the empirical rate equation, –d[C4H6]//dt=(1·86 × 10–3+ 0·681[PPh3])[Ir]0[C4H6]//( 1 + 1·42 × 104[PPh3]) where [Ir]0=[IrH(CO)(PPh3)3]+[IrH3(CO)(PPh3)2].This equation and additional spectrophotometric and kinetic studies of the individual steps in the catalytic cycle are quantitatively interpreted in terms of a mechanism based on the reductive elimination of butenes by Ir(σ-C4H7)H2(CO)(PPh3)2 formed from Ir(π-C4H7)(CO)(PPh3)2 produced by the initial reactions of buta-1,3-diene with both IrH(CO)(PPh3)3 and IrH3(CO)(PPh3)2. The intermediate Ir(π-C4H7)(CO)(PPh3)2 has been isolated and characterised. Rate data for the hydrogenation of ethylene catalysed by the same system have also been quantitatively interpreted by a fundamentally similar mechanism based on the formation of Ir(σ-C2H5)(CO)(PPh3)2 and its subsequent unimolecular decomposition.