期刊
INORGANIC CHEMISTRY
卷 48, 期 2, 页码 588-597出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic801561x
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资金
- Deutsche Forschungsgemeinschaft [SPP 1191]
- Chair of Separation Science & Technology, University of Erlangen-Niirnberg
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][NTf2] is 2000 times higher than the one measured in [emim][EtOSO3]. This difference is much larger than observed for a neutral entering nucleophile studied before.
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