1663-45-2Relevant articles and documents
PH-Switchability and Second-Order Nonlinear Optical Properties of Monocyclopentadienylruthenium(II)/iron(II) Tetrazoles/Tetrazolates: Synthesis, Characterization, and Time-Dependent Density Functional Theory Calculations
Florindo, Pedro R.,Costa, Paulo J.,Piedade,Robalo, M. Paula
, p. 6849 - 6863 (2017)
Tetrazole/tetrazolate monocyclopentadienyliron(II) and ruthenium(II) compounds of general formulas [(η5-C5H5)M(dppe)(N4(H)CC6H4NO2)][PF6]/[(η5-C5H5)M(dppe)(N4CC6H4NO2)] were investigated for their pH-switching second-order nonlinear optical (SONLO) properties. Compounds [(η5-C5H5)M(dppe)(N4CC6H4NO2)] (M = Fe, Ru) and compound [(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)][PF6] were fully characterized by (1H-, 13C-, 31P-) NMR, cyclic voltammetry, and elemental analysis, and compounds [(η5-C5H5)Fe(dppe)(N4CC6H4NO2)] and [(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)][PF6] were further characterized by single-crystal X-ray diffraction; the synthesis of [(η5-C5H5)Fe(dppe)(N4(H)CC6H4NO2)][PF6] was unsuccessful. Time-dependent density functional theory calculations were performed using PBE0 and CAM-B3LYP functionals to evaluate the first hyperpolarizability (βtot) of the tetrazole/tetrazolate complexes and for a detailed analysis of the experimental data. Both functionals predict (i) high first hyperpolarizabilities for the tetrazolate complexes [(η5-C5H5)M(dppe)(N4CC6H4NO2)], with βtot[Ru] ≈ 1.2βtot[Fe], and (ii) a 3-fold reduction in βtot[Ru] upon protonation, in complex [(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)]+, forecasting [(η5-C5H5)Ru(dppe)(N4CC6H4NO2)]/[(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)]+ complexes as on/off, pH-switchable SONLO forms.
Structure of diiodine adducts of some di- and tri-tertiaryphosphines in the solid state and in solution
Bricklebank, Neil,Godfrey, Stephen M.,McAuliffe, Charles A.,Deplano, Paula,Mercuri, Marie L.,Sheffield, Joanne M.
, p. 2379 - 2382 (1998)
A series of ditertiaryphosphine-tetraiodine adducts R2P(I2)(CH2)nP(I2)R 2 (R = Ph, n = 1-4; R = PhCH2 or o-CH3C6H4, n = 2) and two tritertiaryphosphine-hexaiodine adducts, PhP(CH2CH2PPh2)2I6 and CH3C(CH2-PPh2)3I6 have been prepared and characterised by 31P-{H} solution NMR and Raman spectroscopy. In the case of Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4), 31P-{H} NMR magic angle spinning NMR spectroscopy has been used to investigate the nature of the compounds in the solid state. In agreement with our previous extensive studies on the monophosphine derivatives, R3PI2, the tetraiododiphosphine compounds Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4) isolated from diethyl ether contain molecular four-co-ordinate phosphorus centres onto which the diiodine is bound as a linear spoke, as indicated by their 3IP-{H} NMR shifts obtained in CDCl3 solution. Again, in agreement with our previous solution studies of the monophosphine derivatives R3PI2, the diphosphine-tetraiodine adducts completely ionise in CDCl3 solution to produce the ionic compounds [R2P(I)(CH2)nP(I)R2]2I; the solution 31P-{H} NMR shifts are very similar to analogous solution shifts previously assigned to [R3PI]I. The Raman band assignable to v(P-I) has been identified for the compounds and a further band at lower frequency has been observed and assigned to v(I-I). Although the solid-state NMR spectra of the triphosphine-hexaiodine adducts were not recorded, a band assignable, to v(I-I) was observed in the Raman spectrum, suggesting the molecular four-co-ordinate spoke structure also prevails for these hexaiodotritertiaryphosphine compounds in the solid state. From solution 31P-{H} NMR shifts these adducts also appear to ionise in CDCl3 solution.
A mild and efficient CsOH-promoted synthesis of ditertiary phosphines
Honaker, Matthew T.,Salvatore, Ralph Nicholas
, p. 277 - 283 (2004)
A mild and efficient method for the synthesis of ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves, and DMF, various dihalides were coupled with diphenylphosphine at room temperature, and the results have demonstrated that this methodology offers a general synthetic procedure producing a variety of ditertiary phosphines in high yields.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts
Kapu?niak, ?ukasz,Plessow, Philipp N.,Trzybiński, Damian,Wo?niak, Krzysztof,Hofmann, Peter,Jolly, Phillip Iain
, p. 693 - 701 (2021/04/06)
The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.
Reversing Lewis acidity from bismuth to antimony
Balasubramaniam, Selvakumar,Jemmis, Eluvathingal D.,Kumar, Sandeep,Sharma, Deepti,Venugopal, Ajay
supporting information, p. 8889 - 8892 (2021/09/10)
Investigations on the boundaries between the neutral and cationic models of (Mesityl)2EX (E = Sb, Bi and X = Cl?, OTf?) have facilitated reversing the Lewis acidity from bismuth to antimony. We use this concept to demonstrate a higher efficiency of (Mesityl)2SbOTf(Mesityl)2BiOTf in the catalytic reduction of phosphine oxides to phosphines. The experiments supported with computations described herein will find use in designing new Lewis acids relevant to catalysis.
Preparation technology of bis(dibenzyl)phosphorane
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Paragraph 0015, (2019/08/06)
The invention provides a preparation technology of bis(dibenzyl)phosphorane and belongs to the technical field of synthesis of organic matters. The technology comprises the following steps: taking metallic lithium, triphenylphosphine and water to react to generate dibenzylphosphorane; taking the dibenzylphosphorane to react with dihalogenohydrocarbon to generate the bis(dibenzyl)phosphorane. According to a production technology, an intermediate product and an intermediate byproduct do not need to be separated; the technology is simple in technological operation, low in raw material cost and high in yield and can be used for producing the low-cost and high-quality bis(dibenzyl)phosphorane.
Mild Reduction of Phosphine Oxides with Phosphites To Access Phosphines
Li, Peng,Wischert, Raphael,Métivier, Pascal
supporting information, p. 15989 - 15992 (2017/11/01)
A new method for the iodine-catalyzed reduction of phosphine oxides with phosphites at room temperature is reported. The mild reaction conditions, scalability, and simple purification requirements render it a method of choice for the large-scale production and facile regeneration of a variety of phosphines. Mechanistic studies, supported by DFT calculations of the oxygen transfer between the starting phosphine oxide and the phosphite reagent, are also presented. Such transmutations of phosphorus species were previously unknown.
Synthesis of bis(trithio)phosphines by oxidative transfer of phosphorus(i)
Kosnik, Stephanie C.,Nascimento, Maxemilian C.,Rawson, Jeremy M.,Macdonald, Charles L. B.
, p. 9769 - 9776 (2017/08/10)
The synthesis of novel bis(trithio)phosphines is achieved by oxidative addition of tetrathiocins to the phosphorus(i) reagent [PIdppe][Br] in good yields under ambient conditions. These bis(trithio)phosphines and the related intermediate diphosphine species are characterized by X-ray diffraction and multinuclear NMR and a mechanism is proposed for the formation of these molecules. In contrast, the related reaction with diphenyldisulfide produces a mononuclear tris(phenylthio)phosphine.
Raney-Ni reduction of phosphine sulfides
Demchuk, Oleg M.,?wierczyńska, Wioletta,Dziuba, Kamil,Frynas, S?awomir,Flis, Anna,Pietrusiewicz, K. Micha?
, p. 64 - 68 (2016/12/24)
A variety of tertiary phosphine sulfides have been reduced by Raney-Ni to give the corresponding phosphineswith high efficiency and undermild conditions. Alkyl, aryl, acyclic, cyclic, aswell as sterically crowded phosphine sulfides are reduced with equal facility. Optically active P-stereogenic phosphine sulfides are reduced stereospecifically with clean retention of configuration at P. Reductions of unsaturated phosphinesulfides is not fully chemoselective and takes place with concomitant partial reduction of the double bond. Clean reduction of the unsaturated phosphine sulfides to the corresponding fully saturated phosphines can be achieved in one step by running the reduction under H2atmosphere (balloon).
