1,3,2-Diheterophospholane complexes: access to new tuneable precursors of phosphanoxyl complexes and P-functional polymers

Abstract

Synthesis of a testbed of P–H functional diheterophospholane complexes (3 and 6a,b) with no or little steric bulk at the α-position was achieved using [NEt₄][WH(CO)₅] as a combined reductant and complexation reagent. Reaction with TEMPO leads to P-OTEMP substituted tungsten complexes (4 and 7a,b) possessing different thermostabilities towards N–O bond cleavage. The transient phosphanoxyl complexes obtained were used for the polymerisation of styrene and acrylonitrile. DFT calculations were performed on the formation of various open-shell complexes and Loewdin spin density distributions.