posted on 2015-09-08, 00:00authored byRafał Grubba, Anna Ordyszewska, Kinga Kaniewska, Łukasz Ponikiewski, Jarosław Chojnacki, Dietrich Gudat, Jerzy Pikies
The
reactivity of an anionic phosphanylphosphinidene complex of tungsten(VI),
[(2,6-i-Pr2C6H3N)2(Cl)W(η2-t-Bu2PP)]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-Bu2PP)]. 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-Bu2PP 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.