7803-51-2Relevant articles and documents
Kinetics of phosphine hydroxymethylation with formaldehyde
Grekov,Novakov
, p. 358 - 366 (2006)
The kinetics of phosphine hydroxymethylation with formaldehyde is studied. In the absence of a catalyst, phosphine reacts slowly with formaldehyde under normal conditions. Taken separately, amines, hydrochloric acid, and nickel chloride have a low catalytic activity, but the addition of a primary aliphatic amine to nickel chloride effectively increases the hydroxymethylation rate. A probable reaction mechanism is suggested. MAIK Nauka/ Interperiodica 2006.
Chapman, D. L.
, p. 734 - 747 (1899)
Wiles, D. M.,Winkler, C. A.
, p. 902 - 903 (1957)
West, C. A.
, p. 923 - 929 (1902)
Electrolytic formation of phosphine from red phosphorus in aqueous solutions
Shalashova,Smirnov,Nikolashin,Turygin,Khudenko,Brekhovskikh,Fedorov,Tomilov
, p. 236 - 241 (2006)
Data are presented on the current-voltage behavior of red phosphorus suspensions at gold, platinum, lead, and cadmium cathodes in a 1.0 M Na 2CO3 solution. In experiments with a red phosphorus suspension in alkaline solutions, the fo
Evers, E. C.,Finn, J. M.
, p. 559 - 563 (1953)
Martin, D. R.,Dial, R. E.
, p. 852 - 856 (1950)
Organoactinide Phosphine/Phosphite Coordination Chemistry. Facile Hydride-Induced Dealkoxylation and the Formation of Actinide Phosphinidene Complexes
Duttera, Michael R.,Day, Victor W.,Marks, Tobin J.
, p. 2907 - 2912 (1984)
This contribution reports a study of the reaction of the organoactinide hydrides (Cp'2MH2)2 (Cp'=η5-(CH3)5C5, M=Th,U) with trimethyl phosphite.Quantitative transposition of hydryde and methoxide ligands occurs to yield the corresponding Cp'2M(OCH3)2 complexes (synthesized independently from Cp'2MCl2 and NaOCH3) and the phosphinidene-bridged methoxy complexes 2PH.The reaction is considerably more rapid for M=U than for M=Th.The new compounds were characterized by elemental analysis, 1H and 31P NMR, infrared spectroscopy, magnetic susceptibility, and D2O hydrolysis.The molecular structure of 2PH has been determined by single-crystal X-ray diffraction techniques.It crystallizes in the monoclinic space group P2/n with a=13.926(3) Angstroem, b=10.765(3) Angstroem, c=15.282(4) Angstroem, β=107.63(2) deg, and Z=2.Full-matrix least-squares refinement of the structural parameters for the 24 independent anisotropic non-hydrogen atoms has converged to R1 (unweighted, based on F) = 0.041 for 1677 independent absorption-corrected reflections having 2ΘMoKα3?(I).The 2PH molecule has C2 symmetry, with the μ-PH2- ligand lying on a crystallographic twofold axis.The coordination geometry about each uranium ion is of the typical pseudotetrahedral Cp'2M(X)Y type, with U-P=2.743(1) Angstroem, U-O=2.046(14) Angstroem, U-P-U=157.7(2) deg, and U-O-C(methyl)=178(1) deg.Evidence is presented that other >P-OR linkages react in a similar manner.
Langmuir,Mackay
, p. 1708 (1914)
Baudler, M.,Schmidt, L.
, p. 577 - 578 (1959)
Expedient Route to Chalcogenophosphinates with Glucose Moieties via Todd-Atherton-Like Coupling between Secondary Phosphine Chalcogenides and Diacetone- d -Glucose in the CCl4/Et3N System
Volkov, Pavel A.,Ivanova, Nina I.,Gusarova, Nina K.,Sukhov, Boris G.,Khrapova, Kseniya O.,Zelenkov, Lev E.,Smirnov, Vladimir I.,Borodina, Tatyana N.,Vakul'Skaya, Tamara I.,Khutsishvili, Spartak S.,Trofimov, Boris A.
, p. 329 - 334 (2015)
Secondary phosphine chalcogenides react with diacetone-d-glucose (DAG) in the system CCl4/Et3N (70°C, 4-24 h) to afford DAG chalcogenophosphinates in up to 79% yield, thus paving a short way to optically active chalcogenophosphinates with glucose moieties. As an example, a mild regioselective hydrolysis (70 °C, aqueous MeCOOH) of DAG bis(2-phenylethyl)selenophosphinate) obtained leads to monoacetone-d-glucose bis(2-phenylethyl)selenophosphinate.
Evers, C.,Street, E. H.
, p. 5726 - 5730 (1956)
Street, E. H.,Gardner, D. M.,Evers, E. C.
, p. 1819 - 1822 (1958)
Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
Cammarata, Jose,Gschwind, Ruth M.,Lennert, Ulrich,Rothfelder, Robin,Scott, Daniel J.,Streitferdt, Verena,Wolf, Robert,Zeitler, Kirsten
supporting information, p. 24650 - 24658 (2021/10/14)
Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
Generation of a π-Bonded Isomer of [P4]4? by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3
Aldridge, Simon,Ellwanger, Mathias A.,Heilmann, Andreas,Roy, Matthew M. D.
supporting information, p. 26550 - 26554 (2021/11/16)
By employing the highly reducing aluminyl complex [K{(NON)Al}]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), we demonstrate the controlled formation of P42? and P44? complexes from white phosphorus, and chemically reversible inter-conversion between them. The tetra-anion features a unique planar π-bonded structure, with the incorporation of the K+ cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P44?fragment. This complex is extremely reactive, acting as a source of P3?: exposure to ammonia leads to the release of phosphine (PH3) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P4 and NH3 (>5 kbar and >250 °C).
Dual Role of Doubly Reduced Arylboranes as Dihydrogen- and Hydride-Transfer Catalysts
Von Grotthuss, Esther,Prey, Sven E.,Bolte, Michael,Lerner, Hans-Wolfram,Wagner, Matthias
supporting information, p. 6082 - 6091 (2019/04/17)
Doubly reduced 9,10-dihydro-9,10-diboraanthracenes (DBAs) are introduced as catalysts for hydrogenation as well as hydride-transfer reactions. The required alkali metal salts M2[DBA] are readily accessible from the respective neutral DBAs and Li metal, Na metal, or KC8. In the first step, the ambiphilic M2[DBA] activate H2 in a concerted, metal-like fashion. The rates of H2 activation strongly depend on the B-bonded substituents and the counter cations. Smaller substituents (e.g., H, Me) are superior to bulkier groups (e.g., Et, pTol), and a Mes substituent is even prohibitively large. Li+ ions, which form persistent contact ion pairs with [DBA]2-, slow the H2-addition rate to a higher extent than more weakly coordinating Na+/K+ ions. For the hydrogenation of unsaturated compounds, we identified Li2[4] (Me substituents at boron) as the best performing catalyst; its substrate scope encompasses Ph(H)C=NtBu, Ph2C=CH2, and anthracene. The conversion of E-Cl to E-H bonds (E = C, Si, Ge, P) was best achieved by using Na2[4]. The latter protocol provides facile access also to Me2Si(H)Cl, a most important silicone building block. Whereas the H2-transfer reaction regenerates the dianion [4]2- and is thus immediately catalytic, the H--transfer process releases the neutral 4, which has to be recharged by Na metal before it can enter the cycle again. To avoid Wurtz-type coupling of the substrate, the reduction of 4 must be performed in the absence of the element halide, which demands an alternating process management (similar to the industrial anthraquinone process).