Chlorine Dioxide - Structure and Bonding

Structure and Bonding

The molecule ClO2 has an odd number of valence electrons and it is therefore a paramagnetic radical. Its electronic structure has long baffled chemists because none of the possible Lewis structures is very satisfactory. In 1933 L.O. Brockway proposed a structure that involved a three-electron bond. Chemist Linus Pauling further developed this idea and arrived at two resonance structures involving a double bond on one side and a single bond plus three-electron bond on the other. In Pauling's view the latter combination should represent a bond that is slightly weaker than the double bond. In molecular orbital theory this idea is commonplace if the third electron is placed in an anti-bonding orbital. Later work has confirmed that the HOMO is indeed an incompletely-filled orbital.

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