67857-60-7Relevant academic research and scientific papers
Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl, and amino substituents
Szynkiewicz, Natalia,Ponikiewski, ?ukasz,Grubba, Rafa?
supporting information, p. 16885 - 16894 (2019/01/03)
We present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via a salt metathesis reaction of halophosphanes with metal phosphides in high yield. We vastly expanded this group of compounds by obtaining the first mono- A nd tri-amino-substituted systems. The structures of the isolated compounds were characterized by NMR spectroscopy and X-ray diffraction. The isolated unsymmetrical diphosphanes have no tendency to rearrange to the corresponding symmetrical species. Additionally, we proposed the general classification of diphosphanes based on the number of different groups attached to phosphorus atoms and their distribution within a molecule. To investigate the impact of substituents on the properties of P-centers and a molecule as a whole, we conducted a DFT study on the electronic and steric properties of the obtained systems. The experimental and theoretical results can be very useful for designing P-P systems with desired properties.
Reactivity of Phosphanylphosphinidene Complex of Tungsten(VI) toward Phosphines: A New Method of Synthesis of catena-Polyphosphorus Ligands
Grubba, Rafa?,Ordyszewska, Anna,Kaniewska, Kinga,Ponikiewski, ?ukasz,Chojnacki, Jaros?aw,Gudat, Dietrich,Pikies, Jerzy
, p. 8380 - 8387 (2015/09/21)
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).
