Reactivity of Phosphanylphosphinidene Complex of Tungsten(VI) toward Phosphines: A New Method of Synthesis of catena-Polyphosphorus Ligands

Article abstract of DOI:10.1021/acs.inorgchem.5b01063

The reactivity of an anionic phosphanylphosphinidene complex of tungsten(VI), [(2,6-i-Pr₂C₆H₃N)₂(Cl)W(η²-t-Bu₂P=P)]Li·3DME toward PMe₃, halogenophosphines, and iodine was investigated. Reaction of the starting complex with Me₃P led to formation of a new neutral phosphanylphosphinidene complex, [(2,6-i-Pr₂C₆H₃N)₂(Me₃P)W(η²-t-Bu₂P=P)]. Reactions with halogenophosphines yielded new catena-phosphorus complexes. From reaction with Ph₂PCl and Ph₂PBr, a complex with an anionic triphosphorus ligand t-Bu₂P-P^(-)-PPh₂ was isolated. The main product of reaction with PhPCl₂ was a tungsten(VI) complex with a pentaphosphorus ligand, t-Bu₂P-P^(-)-P(Ph)-P^(-)-P-t-Bu₂. Iodine reacted with the starting complex as an electrophile under splitting of the P-P bond in the t-Bu₂P=P unit to yield [(1,2-η-t-Bu₂P-P-P-t-Bu₂)W(2,6-i-Pr₂C₆H₃N)₂Cl], t-Bu₂PI, and phosphorus polymers. The molecular structures of the isolated products in the solid state and in solution were established by single crystal X-ray diffraction and NMR spectroscopy. (Chemical Equation Presented).