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

Trends in the properties of normal valent and multivalent halogen-oxygen bonding are examined for the isomers of the halogen polyoxide families of the types (YXO2) and (YXO3), Y = Cl, Br, I, H, CH 3 , 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. In the model presented, halogen hypervalence is interpreted to be the result of partial p → d promotion of lone-pair valence electrons followed by the formation of two, four, or six additional pd hybrid bonds around the halogen atom.