13598-36-2Relevant articles and documents
Kinetics and Mechanism of the Oxidation of Phosphinic, Phenylphosphinic, and Phosphorous Acids by Pyridinium Fluorotrioxochromate(VI)
Moondra, Anu,Mathur, Abha,Banerji, Kalyan K.
, p. 2697 - 2700 (1990)
Oxidation of the lower phosphorus oxyacids by results in the formation of corresponding oxyacids in the higher valence states.The reaction is first order with respect to the oxidant concentration.A Michaelis-Menten type kinetics was observed with respect to the substrate, indicating the formation of a complex in a pre-equilibrium.The formation constants and the rates of disproportionation of the complexes have been evaluated at different temperatures.The reaction exhibits a substantial primary kinetic isotope effect.The rates in 19 different organicsolvents have been analysed using Kamlet-Taft and Swain equations.It has been found that the cation-solvating power of the solvents plays an important role.It is proposed that the 'inactive ' tautomer of the phosphorus oxyacids is the reactive reductant, and that transfer of a hydride ion from the P-H bond to the oxidant in the rate-determining step occurs.
Kinetics and mechanisms of electron-transfer reactions of bismuth(V) in aqueous acidic perchlorate-fluoride media. Part 1. Oxidation of hypophosphorous acid
Inani, Krishnadass M.,Sharma, Prem Dutt,Gupta, Yugul Kishore
, p. 2571 - 2574 (1985)
Solutions of bismuth(V) from NaBiO3 have been obtained in 1.0 mol dm-3 HClO4 and 1.5 mol dm-3 HF with a view to studying the redox system involving BiV and H3PO2.The reaction is first order in the concentration of each of BiV, H3PO2, and H+.It is catalysed by BiIII through complex formation with the reactive species HBiF6.The rate law (i) holds where Kp is the protonation constant of - and K the complex formation constant between BiV and BiIII.The values of Kpk and K were found to be 0.125+/-0.015 dm6 mol-2 s-1 and 45+/-6 dm3 mol-1 respectively at 35 deg C and I = 2.0 mol dm-3, k' and k are the second-order rate constants for the reaction between HBiF6 and H3PO2, and the complex and H3PO2 respectively.Bismuth(V) does not absorb in the u.v. region but BiIII does, the wavelength depending on the source of BiIII and the medium.
The relative hydrolytic reactivities of pyrophosphites and pyrophosphates
Mistry, Dharmit,Powles, Nicholas
, p. 5727 - 5733 (2013)
The pH-rate profiles for the hydrolysis of pyrophosphate (PP(v)) and pyrophosphite (PP(iii), pyro-di-H-phosphonate) are a complex function of pH, reflecting the different ionic species and their relative reactivities. PP(iii) is more reactive than PP(v) at all pHs and only PP(iii) shows a hydroxide-ion reaction at high pH, so it is 1010-fold more reactive than PP(v) in 0.1 M NaOH. The pKa2 of PP(iii) ～0.44, so the dominant species at pH's > 1 is the di-anion PP(iii)2-. Although there is no observable (NMR or ITC) binding of Mg2+ to the PP(iii) di-anion there is a modest increase in the rate of hydrolysis of PP(iii) by Mg2+. PP(iii) is neither a substrate nor an inhibitor of pyrophosphatase, the enzyme that efficiently catalyses the hydrolysis of PP(v).
Kinetics and Mechanism of Oxidation of Phosphinic, Phenylphosphinic, and Phosphonic Acids by Pyridinium Chlorochromate
Seth, Monila,Mathur, Abha,Banerji, Kalyan K.
, p. 3640 - 3643 (1990)
Oxidation of the lower oxyacids of phosphorus by pyridinium chlorochromate (PCC) results in the formation of the corresponding higher oxyacids of phosphorus.The reaction is of first order with respect to PCC and the oxyacid.The reaction is catalyzed by hydrogen ions, kobs = a + b.The reaction exhibited a substantial primary kinetic isotope effect.The rates in 19 different organic solvents have been analyzed using Kamlet-Taft's and Swains's equations.It has been found that the cation-solvating power of the solvents plays a predominant role.It is proposed that the "inactive" tautomer of the phosphorus oxyacids is the reactiv e species.Transfer of a hydride ion from the P-H bond to PCC, in the rate-determining step, has been proposed.
31PNMR study on the reactions of amino acids and sugar derivatives with pyrophosphorous acid as a possible prebiotic phosphonylating agent
Seio, Kohji,Shiozawa, Takashi,Sugiyama, Daiki,Ohno, Kentaro,Tomori, Takahito,Masaki, Yoshiaki
, p. 905 - 911 (2019)
Phosphorus is an essential element in living organisms. Evaluating prebiotic processes that lead to phosphorylated biomolecules is an important step toward understanding the origin of life. Schreibersite ([Fe,Ni]3P) is a meteoritic phosphorus mineral which releases various phosphorus species reactive toward biomolecules. We studied the reactions between biomolecules and pyrophosphorus acid (H4P2O5), which is a phosphorous acid derivative released from schreibersite. The reactions between pyrophosphorous acid and molecules having hydroxy groups were carried out under mild alkaline conditions. Notably, some biologically important molecules such as L-serine, L-tyrosine, L-threonine, D-ribose, and D-glyceraldehyde reacted with pyrophosphorous acid to give corresponding phosphonates. These results suggested that if schreibersite and the biomolecules co-existed in the prebiotic earth, they formed the phosphonates which were able to play roles as surrogates or precursors of phosphorylated biomolecules.
Oxidation of white phosphorus by peroxides in water
Abdreimova,Akbaeva,Polimbetova
, p. 1873 - 1876 (2017)
A mixture of hypophosphorous, phosphorous, and phosphoric acids is formed during the anaerobic oxidation of white phosphorus by peroxides [ROOН; R = Н, 3-ClC6H4CO, (СН3)3С] in water. The rate of reactions grows considerably upon adding nonpolar organic solvents. The activity series of peroxides and solvents are determined experimentally. NMR spectroscopy shows that the main product of the reaction is phosphorous acid, regardless of the nature of the peroxide and solvent. A radical mechanism of oxidation of white phosphorus by peroxides in water is proposed. It is initiated by the homolysis of peroxide with the formation of НO? radicals that are responsible for the homolytic opening of phosphoric tetrahedrons. Further oxidation and stages of the hydrolysis of intermediate phosphorus-containing compounds yield products of the reaction.
Electrochemical generation of P4 2- dianion from white phosphorus
Yakhvarov,Gorbachuk,Khayarov, Kh. R.,Morozov,Rizvanov, I. Kh.,Sinyashin
, p. 2423 - 2427 (2014)
Electrochemical reduction of elemental (white) phosphorus in an undivided cell equipped with a sacrificial metal anode (Al, Co, Nb, Sn) results in the formation of the reduced form of white phosphorus, P4 2- dianion, which was detected in solution by 31P NMR spectroscopy.
New experimental data and mechanistic studies on the bromate-dual substrate-dual catalyst batch oscillator
Szalai, Istvan,Kurin-Csoergei, Krisztina,Horvath, Viktor,Orban, Miklos
, p. 6067 - 6072 (2006)
The bromate-hypophosphite-acetone-Mn(II)-Ru(bpy)32+ batch oscillator was recently suggested for studying two-dimensional pattern formation. The system meets all major requirements that are needed for generation of good quality traveling waves in a thin solution layer. The serious drawback of using the system for studying, temporal and spatial dynamical phenomena is its unknown chemical mechanism. In order to develop a mechanism that explains the observed long-lasting batch oscillations the bromate-hypophosphite-acetone-Mn(II)-Ru(bpy)32+ oscillator was revisited. We studied the dynamics both in the total system and in some composite reactions, and kinetic measurements were carried out in three subsystems. From the new experimental results we concluded that the two oscillatory sequences observed in the full system are originated from two oscillatory subsystems, the Mn(II)-catalyzed bromate-hypophosphite-acetone and the Ru(bpy)32+-catalyzed bromate-bromoacetone reactions. Here we propose a mechanism which is capable of simulating the dynamical features that appeared in the complex system.
The first water-soluble tetraphosphorus ruthenium complex. Synthesis, characterization and kinetic study of its hydrolysis
Caporali, Maria,Gonsalvi, Luca,Kagirov, Rustam,Mirabello, Vincenzo,Peruzzini, Maurizio,Sinyashin, Oleg,Stoppioni, Piero,Yakhvarov, Dmitry
, p. 67 - 73 (2012)
Reaction of the water-soluble complex [CpRu(TPPMS)2Cl] (1) [TPPMS = sodium salt of m-monosulfonated triphenylphosphine, Ph 2P(m-C6H4SO3Na)] with 1 equiv of white phosphorus in the presence of TlPFsub
Kinetics and mechanisms of reactions of alkyl hydroperoxides with methylrhenium oxides
Brittingham, Kimberly A.,Espenson, James H.
, p. 744 - 750 (1999)
Aqueous methyldioxorhenium (MDO), prepared from methyltrioxorhenium (MTO) and hypophosphorous acid, abstracts an oxygen atom from tertiary alkyl hydroperoxides. This regenerates MTO and forms the tertiary alcohol with rate constants 3.71 × 104 L mol-1 s-1 (t-BuOOH) and 3.47 × 104 L mol-1 s-1 (t-AmOOH) at 25.0 °C in aqueous 1.0 M HOTf. MDO reacts with hydrogen peroxide first to form MTO, k = 3.36 × 104 L mol-1 s-1, which subsequently reacts with more hydrogen peroxide to form peroxorhenium complexes. In a separate study, the concomitant slow decomposition of alkyl hydroperoxides and MTO (to ReO4-) was investigated. The rate law is v = k[MTO][RCMe2OOH]/[H+], with k = 7.4 × 10-5 s-1 (R = Me) and k = 8.4 × 10-5 s-1 (R = Et) at 25.0 °C in aqueous solution at μ 1.0 M. 1H NMR spectroscopy and GC revealed organic products suggestive of radical reactions. The products from t-BuOOH are acetone, methanol, tert-butyl methyl ether, methane, ethane, and rerf-butyl methyl peroxide. With CH2DReO3, it could be shown that both t-BuOOH and MTO were sources of the methane. The rate of decomposition of MTO shows an inverse-first-order dependence on [H+] throughout the range pH 1-6.42.
