Abstract
It is shown from an analysis of data on the structure and properties of tetrahalomethanes CX4, where X = Cl, Br, I, that their chemical behaviour in many respects depends on the energy accessibility of the lowest unoccupied molecular orbital, which is the antibonding analogue of a bonding orbital of σ-type. This characteristic is responsible for, on the one hand, the occurrence of intramolecular interactions between halogen atoms and, on the other hand, their electrophilic properties in reactions with electron donors.
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