Fast substitution reactions of Pt(II) in different ionic liquids. reactivity control by anionic components.

The effect of several imidazolium-based ionic liquids on the rate and mechanism of the substitution reaction of Pt(terpyridine)Cl with thiocyanate was investigated as a function of thiocyanate concentration and temperature under pseudo-first-order conditions using stopped-flow and other kinetic techniques. The obtained rate constants and activation parameters showed good agreement with the ion-pair stabilization energies between the anions of the ionic liquids and the cationic Pt(II) complex derived from density-functional theory calculations (RB3LYP/LANL2DZp) and with parameters derived from the linear solvation energy relationship set by the Kamlet-Taft beta parameter, which is a measure of a solvent's hydrogen bonding acceptor ability. In general, the substitution reactions followed an associative mechanism as found for conventional solvents, but the observed rate constants showed a significant dependence on the nature of the anionic component of the ionic liquid used as solvent. The second order rate constant measured in [emim][NTf(2)] is 2000 times higher than the one measured in [emim][EtOSO(3)]. This difference is much larger than observed for a neutral entering nucleophile studied before.