Styrene Polymerization under Ambient Conditions by using a Transient 1,3,2‐Diazaphospholane‐2‐oxyl Complex

A combined theoretical and experimental study on the formation and reactivity of a P‐OTEMP (P‐bound TEMPO (TEMPO=2,2,6,6‐tetramethyl‐piperidin‐1‐oxyl)) substituted 1,3,2‐diazaphospholane W(CO)5 complex is presented, including DFT‐based mechanistic details. The complex possesses a thermally labile O−N bond that cleaves homolytically yielding the transient 1,3,2‐diazaphospholane‐2‐oxyl complex [(CO)5W(R2PO.)], which acts as a radical initiator for styrene polymerization under ambient conditions. Ambient styrene polymerization: Synthesis and reactivity of a P‐OTEMP (P‐bound TEMPO) substituted 1,3,2‐diazaphospholane complex is reported. Through homolytic O−N bond cleavage, a short‐lived 1,3,2‐diazaphospholane‐2‐oxyl complex was generated, which acts as a radical initiator for styrene polymerization under ambient conditions. Mechanistic details are revealed by DFT calculations.