512-56-1Relevant articles and documents
Complexation and Chemisorption of Trimethylphosphine on Ni Zeolites
Schoonheydt, Robert A.,Wouwe, Dirk Van,Leeman, Hugo
, p. 2519 - 2530 (1980)
After room temperature saturation of dehydrated NiY with trimethylphosphine two complexes are formed in the supercages.They are identified and quantified by reflectance spectroscopy as 0.92+ per unit cell and 6-8l)3-Ni-PMe3>2+ per unit cell (Ol is a lattice oxygen).The former is diamagnetic and trigonal bipyramidal, the latter is paramagnetic and compressed tetrahedral. 2+ is only stable in excess PMe3, while the mono-phosphine complex is stable to ca. 383 K in vacuo.On NiX only the paramagnetic compressed tetrahedral complex is formed.The ligand field parameters of this complex were calculated.Chemisorption on lattice and extralattice oxygens gives strongly held O=PMe3, O=P(OMe)3 and a range of decomposition products such as CO, CO2, H2O, hydrocarbons and oxygenated P on the surface.These products were qualitatively identified by i.r. and mass spectrometry.
Catalysis of the oxidation of triphenylphosphine and of trimethyl phosphite by hydrogen peroxide in the presence of Fe(III) compounds
Barton, Derek H.R.,Hill, David R.,Hu, Bin
, p. 1711 - 1712 (1997)
The oxidation of triphenylphosphine to the corresponding oxide in pyridine is faster in the presence of Fe(III) compounds, especially FeCl3. Even greater effects are seen for the oxidation of trimethyl phosphite.
Ramirez,F. et al.
, p. 3153 - 3156 (1968)
Photooxidation of Trimethyl Phosphite in Nitrogen, Oxygen, and para-Hydrogen Matrixes at Low Temperatures
Ramanathan,Sundararajan,Gopi,Sankaran
, p. 2121 - 2131 (2017)
(Chemical Equation Presented) Trimethyl phosphite (TMPhite) was photooxidized to trimethyl phosphate (TMP) in N2, O2, and para-H2 matrixes at low temperatures to correlate the conformational landscape of these two molecules. The photooxidation produced the trans (TGG)-rich conformer with respect to the ground state gauche (GGG) conformer of TMP in N2 and O2 matrixes, which has diverged from the conformational composition of freshly deposited pure TMP in the low-temperature matrixes. The enrichment of the trans conformer in preference to the gauche conformer of TMP during photooxidation is due to the TMPhite precursor, which exists exclusively in the trans conformer. Interestingly, whereas the photooxidized TMP molecule suffers site effects possibly due to the local asymmetry in N2 and O2 matrixes, in the para-H2 matrix owing to the quantum crystal nature the site effects were observed to be self-repaired.
Bentrude,W.G.,Darnall,K.R.
, p. 2511 - 2513 (1967)
Photoinduced single electron transfer activation of organophosphines: Nucleophilic trapping of phosphine radical cation
Pandey, Ganesh,Pooranchand, Dinah,Bhalerao
, p. 1745 - 1752 (1991)
Photophysical studies show that organophosphines (1-4) form charge transfer stabilized exciplex with excited singlet 1DCN*. One electron oxidation of phosphines to corresponding radical cation via phosphine... 1DCN* electron donor, acceptor pair dissociation is reported. Phosphine radical cations are lound to react readily with moisture to give phosphine oxides.
Terminal Titanyl Complexes of Tri- and Tetrametaphosphate: Synthesis, Structures, and Reactivity with Hydrogen Peroxide
Stauber, Julia M.,Cummins, Christopher C.
, p. 3022 - 3029 (2017)
The synthesis and characterization of tri- and tetrametaphosphate titanium(IV) oxo and peroxo complexes is described. Addition of 0.5 equiv of [OTi(acac)2]2 to dihydrogen tetrametaphosphate ([P4O12H2]2-) and monohydrogen trimetaphosphate ([P3O9H]2-) provided a bis(μ2,κ2,κ2) tetrametaphosphate titanyl dimer, [OTiP4O12]24- (1; 70% yield), and a trimetaphosphate titanyl acetylacetonate complex, [OTiP3O9(acac)]2- (2; 59% yield). Both 1 and 2 have been structurally characterized, crystallizing in the triclinic P1? and monoclinic P21 space groups, respectively. These complexes contain TiO units with distances of 1.624(7) and 1.644(2) ?, respectively, and represent rare examples of structurally characterized terminal titanyls within an all-oxygen coordination environment. Complexes 1 and 2 react with hydrogen peroxide to produce the corresponding peroxotitanium(IV) metaphosphate complexes [O2TiP4O12]24-(3; 61% yield) and [O2TiP3O9(acac)]2- (4; 65% yield), respectively. Both 3 and 4 have been characterized by single-crystal X-ray diffraction studies, and their solid-state structures are presented. Complex 3 functions as an oxygen atom transfer (OAT) reagent capable of oxidizing phosphorus(III) compounds (P(OMe)3, PPh3) and SMe2 at ambient temperature to result in the corresponding organic oxide with regeneration of dimer 1.
METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
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Paragraph 0023; 0026-0028, (2021/09/27)
PROBLEM TO BE SOLVED: To provide a method whereby, a phosphate compound selected from the group consisting of orthophosphoric acid, phosphonic acid, phosphinic acid, and anhydrides of them is used as raw material and, by one stage reaction, a corresponding phosphoester compound is produced. SOLUTION: To an aqueous solution of a phosphate compound, added is an organic silane or siloxane compound having an alkoxy group or an aryloxy group, and the mixture is subjected to a heating reaction, thereby producing a corresponding phosphoester compound without requiring a catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
Thermally induced structural transformations of linear coordination polymers based on aluminum tris(diorganophosphates)
D?bowski, Maciej,?okaj, Krzysztof,Ostrowski, Andrzej,Zachara, Janusz,Wiecińska, Paulina,Falkowski, Pawe?,Krztoń-Maziopa, Anna,Florjańczyk, Zbigniew
supporting information, p. 16480 - 16491 (2018/12/05)
The thermal transitions of inorganic-organic hybrid polymers composed of linear aluminum tris(diorganophosphate) chains with a general formula of catena-Al[O2P(OR)2]3 (where R = C1-C8 alkyl group or phenyl moiety) have been studied by means of DSC, powder XRD, TGA and TG-QMS, as well as optical spectroscopy. DSC and XRD reveal that most of them undergo reversible structural transformations in the solid state between ?100 and 200 °C caused by the changes in conformation of their organic substituents; however, a translational displacement of the rigid polymeric chains occurs only in the case of the derivative bearing long 2-ethylhexyl groups, which becomes liquid at about 140 °C. The thermal decomposition of the studied polymers begins between 200 and 265 °C depending on the type of organic substituent R decorating their aluminophospate core. TGA combined with mass spectrometry of the evolved gaseous products shows that the pyrolytic decomposition of Al[O2P(OR)2]3 proceeds either through β-elimination of olefin (for compounds with C2-C8 aliphatic ligands), or a homolytic cleavage of the P-OR bond (for methyl and phenyl derivatives); both processes are accompanied by condensation of the newly formed POH groups and liberation of water. Powder XRD, FTIR and SEM analyses of the solid residues indicate that thermolysis of Al[O2P(OR)2]3 accompanied by olefin elimination leads to the formation of condensed aluminum phosphates, mainly aluminum cyclohexaphosphate, exhibiting porous morphology. On the other hand, thermal degradation of methyl or phenyl derivatives results in amorphous aluminophosphate residues, and the latter contains conducting carbonaceous phases.
