IR Spectroscopy of Gas Phase V(CO2)n+ Clusters: Solvation-Induced Electron Transfer and Activation of CO2

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• 作者：Allen M. Ricks ; Antonio D. Brathwaite ; Michael A. Duncan
• 刊名：Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：November 14, 2013
• 年：2013
• 卷：117
• 期：45
• 页码：11490-11498
• 全文大小：372K
• 年卷期：v.117,no.45(November 14, 2013)
• ISSN：1520-5215

文摘

Ion鈥搈olecule complexes of vanadium and COb>2b>, i.e., V(COb>2b>)b>nb>⁺, produced by laser vaporization are mass selected and studied with infrared laser photodissociation spectroscopy. Vibrational bands for the smaller clusters (n < 7) are consistent with COb>2b> ligands bound to the metal cation via electrostatic interactions and/or attaching as inert species in the second coordination sphere. All IR bands for these complexes are consistent with intact COb>2b> molecules weakly perturbed by cation binding. However, multiple new IR bands occur only in larger complexes (n 鈮?7), indicating the formation of an intracluster reaction product whose nominal mass is the same as that of V(COb>2b>)b>nb>⁺ complexes. Computational studies and the comparison of predicted spectra for different possible reaction products allow identification of an oxalate-type Cb>2b>Ob>4b> anion species in the cluster. The activation of COb>2b> producing this product occurs via a solvation-induced metal鈫抣igand electron transfer reaction.