Theoretical Investigation of Halogen-Oxygen Bonding and Its Implications in Halogen Chemistry and Reactivity

[摘要] Trends in the properties of normal valent and multivalent halogen-oxygen bonding are examined for the isomers of the halogen polyoxidefamilies of the types (YXO2) and (YXO3), Y=Cl, Br, I, H,CH3, X=Cl, Br, I. A qualitative model is formulated on the relationship between the X-O bond distance variations, the ionic character of the bonding,and the degree of halogen valence. The relative stability and enthalpy of formation of each species are also suggested to correlate with the ionic nature of the X-O bonding and the electrostatic character of the Y, YO fragments. Inthe model presented, halogen hypervalence is interpreted to be the result of partialp→dpromotion of lone-pair valence electrons followed by the formation oftwo, four, or six additional pd hybrid bonds around the halogen atom.

[学科分类] 物理化学和理论化学