P{H} NMR studies of the nonoxidative chlorination of poly(1,12-dodecane phosphonate) and subsequent coordination and nucleophilic reactions

Quantitative ³¹P{¹H} NMR spectroscopic studies demonstrate that dichloro(2,4,6-tribromophenoxy)(2,2′-biphenoxy)phosphorane, (TBPO)(DP)PCl₂, quantitatively converts poly(1,12-dodecylene phosphonate) into the corresponding poly(1,12-dodecylene chlorophosphite). NMR analysis indicates that the reaction is quantitative and the polymer remains intact. The poly(1,12-dodecylene chlorophosphite) chlorophosphite has been characterized by its reactions with acetonitrilepentacarbonyltungsten(0), W(CO)₅(CH₃CN), and subsequent nucleophilic displacement reactions at the coordinated chlorophosphite group. Quantitative ³¹P{¹H} NMR spectroscopic studies demonstrate that the polymer chain remains intact throughout the coordination and nucleophilic reactions. All of the reactions are quantitative by NMR spectroscopy, the synthesis of the (TBPO)(DP)PCl₂ and the subsequent nonoxidative chlorination reactions can be carried out in one pot, and the byproduct of the reaction does not interfere with the reactions or cleave the polymer chains.