2528-38-3Relevant articles and documents
Acceleration of the Pseudorotation Rates in Pentacoordinated Phosphorus Compounds. Conformational Transmission versus Hexacoordinated Zwitterionic Intermediates
Keijzer, A. E. H. de,Buck, H.M.
, p. 4827 - 4831 (1988)
A variable-temperature 13C NMR study, accompanied by a high-resolution 1H NMR conformational analysis study, on a series of monocyclic oxyphosphoranes is reported.The selected compounds enabled us to study the acceleration of the rates of intramolecular ligand reorganization on pentacoordinated phosphorus.It allowed us to determine whether the enhancement of the reorganization rates was brought about by accelerated pseudorotation due to the conformational transmission effect or by the involvement of hexacoordinated zwitterionic phosphorus intermediates.The results of the study further substantiate the findings that the involvement of such hexacoordinated intermediates is of no importance in the type of oxyphosphoranes studied.
Electrocatalytic eco-efficient functionalization of white phosphorus
Budnikova, Yulia H.,Yakhvarov, Dmitry G.,Sinyashin, Oleg G.
, p. 2416 - 2425 (2007/10/03)
The novel eco-efficient methods to transform white phosphorus into the esters of phosphoric, phosphorous and phosphonic acids, tertiary phosphines and other organophosphorus compounds under conditions of electrochemical catalysis were elaborated. The mechanism of these processes was investigated using the method of cyclic voltammetry and preparative electrolysis.
Oxidative P-O and P-C Coupling of Butanol with Phosphine in the Presence of Oxidizers and Platinum(IV) and Platinum(II)
Dorfman,Polimbetova,Aibasov
, p. 231 - 247 (2007/10/03)
A butanol solution of Na2PtCl6 at 60-80°C in the presence of p-benzoquinone or NaBrO3 is found to rapidly consume even traces of PH3 until complete reduction of benzoquinone to hydroquinone or NaBrO3 to NaBr, respectively. The nature of products depends on the valence state of platinum and the nature of the oxidizer. Without an oxidizer, platinum(IV) is reduced to platinum(II) with formation of tributyl phosphate, the product of P-O coupling of PH3 with BuOH, while platinum(II) is reduced to platinum(0) with formation of butylbis(α-hydroxybutyl)phosphine oxide Bu(α-PrCHOH)2PO, the product of P-C coupling of PH3 with BuOH. In the presence of benzoquinone, which oxidizes Pt(0) to Pt(II), a P-C bond is formed, while in the presence of sodium bromate, which regenerates Pt(II) to Pt(IV), P-O coupling of PH3 with BuOH occurs. The products and principal steps of this new reaction were studied by the methods kinetics, red-ox potentiometry, chemical modeling, inhibition of free-radical reactions, 31P NMR, IR and X-ray photoelectron spectroscopy, X-ray spectral microanalysis, and gas-liquid chromatography. We showed that the P-C coupling of PH3 with BuOH is promoted by platinum(II) complex, while P-O coupling is promoted by platinum(IV) complex. In the key steps the Pt(II) butoxyphosphide complex PtCl3(OBu)(PH2)- arises from reaction of the Pt(II) phosphide complex with platinum(IV). The red-ox decomposition of intermediate complexes leads to formation of phosphinite (BuO)2PH2 and Pt(II), or (α-hydroxybutyl)phosphine and Pt(0). The catalytic cycles are completed by fast steps of oxidative butoxylation of (BuO)PH2 to (BuO)3PO or by α-hydroxybutylation of (PrCHOH)PH2 to Bu(PrCHOH)2PO, and oxidation of Pt(II) to Pt(IV) with bromate or Pt(0) to Pt(II) with benzoquinone, respectively.
