Reactivity of Hydrated Monovalent First Row Transition Metal Ions M+(H2O)n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbo

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• 作者：Christian van der Linde ; Sonja Hemmann ; Robert F. H枚ckendorf ; O. Petru Balaj ; Martin K. Beyer
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：February 14, 2013
• 年：2013
• 卷：117
• 期：6
• 页码：1011-1020
• 全文大小：522K
• 年卷期：v.117,no.6(February 14, 2013)
• ISSN：1520-5215

文摘

The reactions of hydrated monovalent transition metal ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward molecular oxygen, nitrous oxide, and carbon dioxide were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Clusters containing monovalent chromium, cobalt, nickel, or zinc were reactive toward O₂, while only hydrated cobalt was reactive toward N₂O. A strongly size dependent reactivity was observed. Chromium and cobalt react very slowly with carbon dioxide. Nanocalorimetric analysis, ¹⁸O₂ exchange, and collision induced dissociation (CID) experiments were done to learn more about the structure of the O₂ products. The thermochemistry for cobalt, nickel, and zinc is comparable to the formation of O₂^{鈥?/sup> from hydrated electrons. These results suggest that cobalt, nickel, and zinc are forming M2+/O₂鈥?/sup> ion pairs in the cluster, while chromium rather forms a covalently bound dioxygen complex in large clusters, followed by an exothermic dioxide formation in clusters with n 鈮?5. The results show that hydrated singly charged transition metal ions exhibit highly specific reactivities toward O₂, N₂O, and CO₂.}