Direct synthesis of cyclic and polymeric phosphazenes bearing diphenylphosphine groups and their complexes with [W(CO) 5] fragments

Abstract

The reactions of the cyclotriphosphazenes [N 3P 3Cl 6] or [N 3P 3(O 2C 12H 8) 2Cl 2] with the phenolic phosphine PPh 2(C 6H 4-OH) in the presence of Cs 2CO 3 give, respectively, the cyclic phosphazene phosphines [N 3P 3(OC 6H 4PPh 2) 6] ( 1) and [N 3P 3(O 2C 12H 8) 2(OC 6H 4PPh 2) 2] ( 2), very pure and in high yield. The similar reaction with the linear polyphosphazene {[NP(O 2C 12H 8)] 0.65[NPCl 2] 0.35} n in THF gives the diphenylphosphine polymer {[NP(O 2C 12H 8)] 0.65[NP(OC 6H 4PPh 2) 2] 0.35} n ( 3). The phenolic tungsten pentacarbonyl complex {W(CO) 5[PPh 2(C 6H 4-OH)]} reacts in the same way with those cyclic and polymeric phosphazenes to give the corresponding complexes {N 3P 3[OC 6H 4PPh 2-W(CO) 5] 6} ( 4), [N 3P 3(O 2C 12H 8) 2(OC 6H 4PPh 2-W(CO) 5) 2] ( 5), and {[NP(O 2C 12H 8)] 0.65[NP(OC 6H 4PPh 2-W(CO) 5) 2] 0.35} n ( 6).