On metal coordination of neutral open-shell P-ligands focusing on phosphanoxyls, their electron residence and reactivity.

This feature article highlights the discovery and development of phosphanoxyl complex chemistry starting from (neutral) low-coordinate phosphorus radicals and the quest of metal ligation effects. We describe synthesis and reactions of precursors, namely 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) substituted phosphane tungsten(0) complexes. Trapping reactions of transient phosphanoxyl complexes, formed thermal homolytic N-O bond cleavage, as well as their use in radical polymerisations are illustrated, thus revealing an interesting reactivity dichotomy. DFT calculations provide insight into thermal stabilities of precursors and the resulting spin density distributions (SDDs) in these reactive intermediates. Systematic studies on the dependance of the electron delocalisation in phosphanoxyl complexes have been performed examining different substitution pattern at phosphorus and different co-ligand combinations at the tungsten(0) center. Preliminary results on Mn and Fe complexes are reported.