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Oral Sessions
Day 2, June 23（Mon.） 16:40-16:55
Room B (Maesato Center)
- 2B-O3-1640
Masked Reactivity of Hydrated Clusters of Monovalent Manganese Ion: H2O Insertion vs. N2O Activation ― A DFT Investigation
(City U Hong Kong)
oChi-Kit Siu
Mass spectrometric (MS) studies demonstrated that singly charged hydration clusters of manganese ions [Mn(H2O)n]+ were, on one hand, highly reactive toward intracluster water insertion but, on the other hand, inert toward nitrous oxide activation. This contrast in reactivity is rationalized by our theoretical investigation based on density functional theory (DFT) for the interconversion between the pristine Mn(I) monovalent form as a monatomic ion in [MnI(H2O)n]+ and the oxidized Mn(III) trivalent form as a hydride-hydroxide in [HMnIIIOH(H2O)n-1]+, as well as their reactivity toward nitrous oxide activation. Our DFT results show that H2O insertion is kinetically and thermodynamically favorable for n ≥ 8, suggesting that [HMnIIIOH(H2O)n-1]+ is the predominant form, as observed in previous MS experiments. While [MnI(H2O)n]+ is capable of N2O reduction and the process is highly exothermic though, similar reactions are unfavorable with [HMnIIIOH(H2O)n-1]+, which can only form weakly bound adducts with N2O. This work demonstrates the masking effect of water molecules over the high reactivity of the hydrated Mn(I) center and sheds light on the potential roles of water in transition metal systems.