A comparison of orbital interactions in the additions of phosphonyl and acyl radicals to double bonds.

Calculation of the barriers for addition of the H2P(=O) and HC(=O) radicals to alkenes, at the CCSD(T)/aug-cc-pVDZ//BHandHLYP/6-311G** level, indicates that both radicals display ambiphilic behaviour. For the HC(=O) radical this behaviour occurs because a secondary orbital interaction of the type pi*(C=O)<--HOMO acts in conjunction with the primary SOMO<--HOMO interaction to balance the SOMO-->LUMO interaction. For the H2P(=O) radical, on the other hand, the much higher-lying LUMO (the sigma*P-O orbital) allows for only minimal secondary interaction, and this radical's ambiphilic behaviour is therefore reflective of a balance between SOMO-->LUMO and SOMO<--HOMO interactions.