Comparative study of the gas-phase bond strengths of CO2 and N 2O with the halide ions.
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.
Faculty of Engineering, Yamanashi University, Takeda-4, 400, Kofu, Japan.
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Hiraoka
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Aruga
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Fujimaki
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Yamabe