Comparative study of the gas-phase bond strengths of CO2and N2O with the halide ions

✍ Scribed by Kenzo Hiraoka; Kazuo Aruga; Susumu Fujimaki; Shinichi Yamabe

• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 620 KB
• Volume: 4
• Category: Article
• ISSN: 1044-0305
• DOI: 10.1016/1044-0305(93)85043-w

✦ Synopsis

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.