Abstract
An ESR study on three-electron P ∸ S bonds in progressively substituted trialkylphosphine sulfide phosphoranyl radicals R 3ṖSR n−1 n ( n = 0, 1, 2) is presented. The experiments show, in contrast with quantum chemical calculations, that the structure is not seriously affected by the electronegativity of the sulfur fragment. It is concluded that three-electron bonds can be formed in condensed phases, despite an unfavourable balance of the ionization potentials of the fragments involved.
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