Comparative study of the gas-phase bond strengths of CO2 and N2O with the halide ions |
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| Authors: | Kenzo Hiraoka Kazuo Aruga Susumu Fujimaki Shinichi Yamabe |
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| Institution: | 1. Faculty of Engineering, Yamanashi University, Takeda-4, 400, Kofu, Japan
2. Department of Chemistry, Nara University of Education, Takabatake-cho, 630, Nara, Japan
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| Abstract: | Thermodynamic data, δH°n?1,n and δ S°?1, n, for clustering reactions of halide ions X? (X = F, Cl, Br, and I) with N2O were 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, FCO?2, 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—CO?2 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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