A detailed kinetic analysis of rhodium-catalyzed alkyne hydrogenation.

Continuous monitoring using electrospray ionisation mass spectrometry (ESI-MS) shows that Wilkinson's catalyst hydrogenates a charge-tagged alkyne to the corresponding alkene, and at only a marginally slower rate, to the alkane. No rhodium-containing intermediates were observed during the reaction, consistent with the established mechanism which points at the initial dissociation of triphenylphosphine from Rh(PPh₃)₃Cl as being the key step in the reaction. A numerical model was constructed that the closely matched the experimental data, and correctly predicted the response of the reaction to the addition of excess PPh₃.