Reactivity of Phosphanylphosphinidene Complex of Tungsten(VI) toward Phosphines: A New Method of Synthesis of catena-Polyphosphorus Ligands.
The reactivity of an anionic phosphanylphosphinidene complex of tungsten(VI), [(2,6-i-Pr2C6H3N)2(Cl)W(η(2)-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(η(2)-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 Faculty, Department of Inorganic Chemistry, Gdansk University of Technology , G. Narutowicza St. 11/12, Pl-80-233 Gdansk, Poland.
Rafał
R
Grubba
Chemical Faculty, Department of Inorganic Chemistry, Gdansk University of Technology , G. Narutowicza St. 11/12, Pl-80-233 Gdansk, Poland.
Anna
A
Ordyszewska
Chemical Faculty, Department of Inorganic Chemistry, Gdansk University of Technology , G. Narutowicza St. 11/12, Pl-80-233 Gdansk, Poland.
Kinga
K
Kaniewska
Chemical Faculty, Department of Inorganic Chemistry, Gdansk University of Technology , G. Narutowicza St. 11/12, Pl-80-233 Gdansk, Poland.
Łukasz
Ł
Ponikiewski
Chemical Faculty, Department of Inorganic Chemistry, Gdansk University of Technology , G. Narutowicza St. 11/12, Pl-80-233 Gdansk, Poland.
Jarosław
J
Chojnacki
Institut für Anorganische Chemie, Universität Stuttgart , Pfaffenwaldring 55, 70550 Stuttgart, Germany.
Dietrich
D
Gudat
Chemical Faculty, Department of Inorganic Chemistry, Gdansk University of Technology , G. Narutowicza St. 11/12, Pl-80-233 Gdansk, Poland.
Jerzy
J
Pikies