Abstract
Thermodynamic data, ΔH n-1, n o and ΔS n-1, n o, for clustering reactions of halide ions X−(X = F, Cl, Br, and I) with N2Owere measured with a pulsed electron beam high-pressure mass spectrometer. In contrast to the fact that CO2 forms a covalent bond with the fluoride ion to yield the fluoroformate ion, FCO2 −, the interaction between F− and N2O is mainly electrostatic. It was found that the cluster ions F− (N2O)n complete the first shell at n = 6, thus forming an octahedral structure. The difference between F—CO2 − and F− ... N2O is discussed in terms of Coulombic, exchange, and charge-transfer interactions. The X− (N2O)2 clusters (X = Cl, Br and I) are found to be of C2h symmetry, while F− (N2O)2 is of a twisted form and is slightly asymmetric due to a slight participation of covalency (charge transfer) in the core ion F− ... N2O.
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Hiraoka, K., Aruga, K., Fujimaki, S. et al. Comparative study of the gas-phase bond strengths of CO2 and N2O with the halide ions. J Am Soc Mass Spectrom 4, 58–64 (1993). https://doi.org/10.1016/1044-0305(93)85043-W
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DOI: https://doi.org/10.1016/1044-0305(93)85043-W