Solid-state reactions in the carbonylchlorobis(triphenylphosphine)iridium(I)–hydrogen chloride system
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 17,p. 1802-1804
- https://doi.org/10.1039/dt9730001802
Abstract
The kinetics of addition of HCl gas to the solid complex [IrClCO(PPh3)2] to form the trans-chloro-octahedral species have been studied. The rate-controlling step is chemical reaction at the phase boundary, with an activation energy of 37 kJ mol–1 and an entropy change of –184 J K–1 mol–1. The reverse reaction has an activation energy of 51 kJ mol–1 and an entropy change of –176 J K–1 mol–1. Loss of HCl from the cis-chloro-isomer is again controlled by reaction at the phase boundary with an activation energy of 130 kJ mol–1 and an entropy change of –92 J K–1 mol–1. The enthalpy of dehydrochlorination of each isomer has been measured, and mechanistic implications of the results are discussed.Keywords
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