Mechanistic Insight from Activation Parameters for the Reaction of a Ruthenium Hydride Complex with CO2 in Conventional Solvents and an Ionic Liquid

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• 作者：Simon Kern ; Rudi van Eldik
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：July 2, 2012
• 年：2012
• 卷：51
• 期：13
• 页码：7340-7345
• 全文大小：309K
• 年卷期：v.51,no.13(July 2, 2012)
• ISSN：1520-510X

文摘

Detailed kinetic studies were performed on the reaction of [Ru^II(terpy)(bpy)H]⁺ (terpy = 2,2鈥?6鈥?2鈥?terpyridine; bpy = 2,2鈥?bipyridine) with CO₂ in conventional solvents (water, methanol, and ethanol) and in the ionic liquid [emim][NTf₂] ([emim] = 1-ethyl-3-methyl-imidazolium; [NTf₂] = bistrifluoromethylsulfonylamide). Second-order rate constants and activation parameters (螖H, 螖S, and 螖V) were determined for the reaction in all solvents. The second-order rate constants correlate with the acceptor number of the solvent, whereas the activation parameters support the associative nature of the reaction. The results in water, especially the activation entropy (+14 卤 2 J K^鈥? mol^鈥?) and activation volume (鈭?.9 卤 0.6 cm³ mol^鈥?), differ significantly from those found for the other solvents.