四(三苯基氧化膦)二氯稀土(Ⅲ)-三氯化铜(Ⅱ)配合物的合成和谱学性质

合成了通式为[LnCl_2(Ph_aPO)_4][CuCl_3](Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Y)的12种新配合物,X射线衍射结构分析证实[GdCl_2(Ph_2PO)_4][CuCl_3]中Gd(Ⅲ)为六配位畸变八面体形,Cu(Ⅱ)为三配位平面三角形.测定了所有配合物的红外光谱、~(31)P NMR和Cu(Ⅱ)的顺磁共振谱,并对[LnCl_2(Ph_3PO)_4][CuCl_3]的生成进行了讨论.     

Reaction of N-sulfinyltrifluoromethanesulfonamide with triphenylphosphine and triphenylphosphine oxide

The reaction of N-sulfinyltrifluoromethanesulfonamide with triphenylphosphine and triphenylphosphine oxide or of trifluoromethanesulfonamide with dichloro(triphenyl)phosphorane leads to trifluoro-N-(triphenyl-λ⁵-phosphanylidene)methanesulfonamide, which is hydrolyzed to trifluoromethanesulfonamide and triphenylphosphine oxide via the intermediate trifluoro-N-[hydroxy(triphenyl)phosphoranyl]methanesulfonamide.     

Synthesis and studies on dichloro iodo triphenylphosphine oxide nickel(III)

A new compound of nickel(III), [Ni(OPPh₃)Cl₂I] has been prepared by the action of nitrosyl chloride or chlorine gas on [Ni(PPh₃)₂I₂]. Various physical studies of the compound are reported.     

Synthesis and coordination properties of new preorganized ligand on the triphenylphosphine oxide platform

Tris(2-cyanomethoxyphenyl)phosphine oxide was synthesized by the reaction of tris-(2-hydroxyphenyl)phosphine oxide with chloroacetonitrile. Its coordination properties were studied for the complexation with neodymium(iii) and copper(ii) nitrates using vibrational spectroscopy, NMR, and quantum chemical calculations.     

Synthesis and crystal structure of a 1 : 2 adduct of aquatrifluoroboron and triphenylphosphine oxide

A crystalline 1 : 2 adduct of aquatrifluoroboron and triphenylphosphine oxide 1/2[BF₃(H₂O)] · Ph₃PO(I) is synthesized and studied by X-ray diffraction analysis. The crystals are orthorhombic, space group Fdd2, a = 32.283 Å, b = 20.162 Å, c = 10.191 Å, Z = 16. The structure is solved by the direct method and refined by a full-matrix least-squares method in the anisotropic approximation to R = 0.054 against 2528 independent reflections (CAD4 automated diffractometer, MoK). A Ph₃PO molecule has a normal structure. A [BF₃(H₂O)] molecule is randomly disordered relative to axis 2; populations of positions of all its atoms are 0.5. The boron atom has a distorted tetrahedral coordination with a donor-acceptor B-O(w) bond. In crystal, strong hydrogen bonds of the P=OH-O-HO=P type are formed between the H₂O molecule and two Ph₃PO molecules.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 12–16.Original Russian Text Copyright © 2005 by Chekhlov.     

稀土-2,6-吡啶二甲酸-氧化三苯基膦配合物的合成及其荧光性质

稀土离子尤其是Sm,Eu,Tb,Dy因为其良好的荧光性能而得到了广泛的研究和应用[1,2]。吡啶二甲酸和氧化三苯基膦这两种配体有较大范围的共轭π键,在近紫外区又都有较宽的吸收带和较强的吸收峰,与稀土离子配位后可以构成有效的能量传递体系,将它们在近紫外区吸收的能量有效地传递给     

Flame retardant polycyanurate thermosets from the cyanate esters of triphenylphosphine oxide

Three cyanate esters containing phosphorus are synthesized in good overall yields starting from bromoanisoles. Di‐ and tricyanates with meta configuration are most stable while para is less so. The para dicyanate ester isomer is particularly affected by water from the atmosphere. The meta dicyanate ester 2 has good thermal properties with glass transition at 268 °C and char yield of 65% in air at 600 °C. All three phosphorus‐containing cyanate esters are low flammability in an open flame. They make highly combustible cyanate esters resins less flammable simply by blending. Mixing 10 wt% dicyanate ester 2 into bisphenol A or E dicyanate esters makes them rate V‐0. Published 2018.^† J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1100–1110     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

Electroreduction of triphenylphosphine dichloride and the efficient one-pot reductive conversion of phosphine oxide to triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode. Further, the one-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide in acetonitrile with oxalyl chloride and subsequent electrochemical reduction.     

Synthesis and crystal structure of (18-crown-6)(perchlorato-O)(triphenylphosphine oxide)potassium

A new complex, (18-crown-6)(perchlorato-O)(triphenylphosphine oxide)potassium, was synthesized and its structure was studied by X-ray diffraction. The crystals are trigonal: a = 14.419,c = 13.895 Å, Z = 3, space group R3m; the structure was solved by the direct method and refined by the anisotropic full-matrix least-squares method, R = 0.079 on 1930 independent reflections, CAD-4 automated diffractometer, λMoK _α . The structure contains a highly symmetric host-guest complex molecule [K(ClO₄)(18-crown-6)(Ph₃PO)] in position 3m (with three Ph rings of the Ph₃PO ligand and all the O atoms of a crown ligand lying in three m planes). The coordination polyhedron of the K⁺ cation is a distorted hexagonal bipyramid with six O atom of the 18-crown-6 ligand in a base and the O atom of the Ph₃PO ligand and disordered O atom of the ClO ₄ ^? ligand in the axial vertices.     

Synthesis and Crystal Structure of (18-Crown-6)(nitrato)(triphenylphosphine oxide)potassium

A new complex (18-crown-6)(nitrato)(triphenylphosphine oxide)potassium (I) is synthesized, and its crystal structure is studied by X-ray diffraction analysis (space group R3m, a = 14.336 Å, c = 13.776 Å, Z = 3). The structure is solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.034 for 1122 independent reflections (CAD4 automated diffractometer, λ MoK_α radiation). Structure I contains a complex host-guest molecule [K(NO₃)(18-crown-6)(Ph₃PO)] with crystallographic symmetry 3m (three planes m contain three Ph rings of the Ph₃PO ligand and all O atoms of the crown ligand). The coordination polyhedron of the K⁺ cation is a distorted hexagonal bipyramid with all the six O atoms of the crown ligand in the base, the O atoms of the Ph₃PO ligand, and one (or two) O atoms of a disordered NO ₃ ^? ligand in the axial positions.     

Extraction and separation of scandium salicylate with triphenylphosphine oxide

Scandium can be extracted from 5.0 × 10⁻² mol/1 sodium salicylate solution, adjusted to pH 4.0–5.0 with 0.5% triphenylphosphine oxide dissolved in toluene as an extractant. After stripping from the organic phase with 0.5 mol/1 HCl it can be subsequently determined spectrophotometrically with Alizarin Red S. The method permits a separation of Sc(III) from Ti(IV), V(V), Cr(VI), Fe(III), Y(III), La(III), Ce(III), Nd(III) and Sm(III) in synthetic mixtures. The method is fast, simple and selective.     

Extraction and separation of scandium salicylate with triphenylphosphine oxide

Scandium can be extracted from 5.0 × 10^–2 mol/l sodium salicylate solution, adjusted to pH 4.0–5.0 with 0.5% triphenylphosphine oxide dissolved in toluene as an extractant. After stripping from the organic phase with 0.5 mol/l HCl it can be subsequently determined spectrophotometrically with Alizarin Red S. The method permits a separation of Sc(III) from Ti(IV), V(V), Cr(VI), Fe(III), Y(III), La(III), Ce(III), Nd(III) and Sm(III) in synthetic mixtures. The method is fast, simple and selective. Received: 6 May 1996 / Revised: 21 July 1996 / Accepted: 25 July 1996     

Ortho-lithiation of triphenylphosphonio-methylid and,also, triphenylphosphine oxide

While upon treatment with methyl- or butyllithium triphenylphosphonio-methylid ( 1 ) undergoes extensive ligand exchange (leading to 4) it reacts with sec- or tert-butyllithium mainly at the ortho-position exchanging one hydrogen against a lithium atom (to give 3).     

Extraction of palladium from nitrate solution by triphenylphosphine or triphenylphospine oxide in chloroform

It is found that from aqueous nitric acid media, Pd is highly extracted by chloroform solutions containing triphenylphosphine (Ph₃P) and not extracted by triphenylphosphine oxide (Ph₃PO) diluted with chloroform. The effect of diluent, nitric acid molarities, Ph₃P concentration and temperature on palladium extraction by Ph₃P was investigated. Slope analysis of the experimental results indicated that the main extracted species is in the form of Pd(NO₃)₂·2Ph₃P.IR spectrum analysis of the extracted complex indicated the direct extraction of palladium as nitrate and bonding to phosphorus. Extraction of some fission product radionuclides from 2M HNO₃ showed the selective extraction of palladium by Ph₃P in chloroform.     

Nitrato(triphenylphosphine) complexes of the platinum metals; Detection of triphenylphosphine oxide ligands

Reactions of some platinum group metal triphenylphosphine complexes with nitric acid afford nitrato(triphenylphosphine) derivatives in good yield; the complex “Rh(NO₃) (NO)₂(OPPh₃)₂” is positively identified as [Rh(NO₃)₂ (NO) (PPh₃)₂]     

Laser photolysis studies of the reaction of chromium(III) octaethylporphyrin complex with triphenylphosphine and triphenylphosphine oxide

The photoreaction of the chromium(III) octaethylpoprhyrin complex, [Cr(OEP)(Cl)(L)] (L = H2O, Py, OPPh3), in dichloromethane was studied using laser flash photolysis technique. Laser irradiation causes the generation of a coordinately unsaturated intermediate [Cr(OEP)(Cl)], which reacts with ligands in solution to give the parent complex, [Cr(OEP)(Cl)(L)], or a transient species, [Cr(OEP)(Cl)(H2O)], when L = Py or OPPh3. Once produced [Cr(OEP)(Cl)(H2O)] eventually exchanges the axial H2O ligand with L to regenerate [Cr(OEP)(Cl)(L)]. The kinetics of the axial ligand substitution reaction was followed spectrophotometrically, and the ligand-concentration dependence of the ligand exchange rate revealed that the reaction occurs via a limited dissociative mechanism. The photoreaction of [Cr(OEP)(Cl)(OPPh3)] containing excess PPh3 in the bulk solution leads to the unfavorable coordination of the PPh3 molecule to the chromium ion to give a transient complex, [Cr(OEP)(Cl)(PPh3)]. The dynamic and thermodynamic properties of [Cr(OEP)(Cl)(PPh3)] in solution are discussed on the basis of the kinetic parameters of the dissociation and association reactions of the PPh3 ligand together with the steric aspect of the molecular structure of the related complexes.