Electrochemical synthesis of phosphorus esters from white phosphorus in the presence of copper complexes and ethanol

In the presence of white phosphorus the redox potentials of the copper ions change and the potential of the reduction wave of Cu^I/Cu⁰ shifts noticeably toward more positive values. The Cu^I—P₄ complex is characterized by a lower value of the electrochemical gap, that is, higher polarizability and reactivity compared to those of the free Cu^I cation. Phosphorus esters can be synthesized from P₄ and ethanol. The latter is in the composition of the copper(ii) complexes, which act as a catalyst-charge mediator.     

不对称合成中手性磷配体催化剂的研究进展（I）（待续）

评述了作为配体催化剂的手性三配位及四配位磷化合物的合成及其在某些不对称的合反应中的应用。     

Syntheses and structural characterizations of Fe_4S_4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.     

Catalytic phosphorylation of polyfluoroalkanols. 17. Synthesis and the stereochemistry of tris(α-trifluoromethylbenzyl) phosphates

Catalytic phosphorylation of -trifluoromethylbenzyl alcohols with POCl₃ taken in a ratio of 3 : 1 under particular temperature conditions afforded predominantly symmetrical tris(-trifluoromethylbenzyl) phosphates. The latter were obtained as mixtures of two diastereomers with a statistical ratio of the components.     

Crystal structure and luminescence property of ternary terbium p-aminobenzoic acid complexes with different second ligands

Ternary terbium complexes with p-aminobenzoic acid (HL), [TbL₃(DMSO)(H₂O)]₂ (1), [TbL₃(DMF)(H₂O)]₂ (2) and [TbL₃(Bpy)(H₂O)]₂·2H₂O (3) (DMSO=dimethyl sulfoxide, DMF=N, N- dimethylformamide, Bpy=2, 2′- bipyridyl) have been synthesized, and their crystal structures determined. The luminescence properties of these complexes, including both the emission quantum yield and the fluorescence lifetime, have been investigated. The effect of a second ligand on the crystal structure and luminescence property of the ternary terbium p-aminobenzoic acid complexes, and the relationship between luminescence properties and crystal structure, including coordination mode of the L⁻ ligand and the characteristics of a second ligand, are discussed.     

Ligand dynamics and reactivity in trimetallic clusters

The general relationships between trinuclear cluster reactivity and the ligand dynamical processes in these systems are explored. Three specific mechanistic studies are presented: (1) the rate and stereochemistry of ligand addition to ₃-imidoyl complexes, (2) the factors influencing the rate of carbon-hydrogen bond activation in ₃-alkyne complexes, and (3) the origin of anomalously large kinetic deuterium isotope effect in metal to ligand and ligand to metal hydrogen transfer in trinuclear and binuclear complexes. In all three cases, the current state of the mechanistic studies are summarized and the possible rate of specific ligand dynamical processes in controlling the mechanism are put forth.     

Synthesis and Crystal Structure of a Vanadium(Ⅴ) Complex with 2-Hydroxy-1-naphthaldehyde Isonicotinoyl Hydrazone

The mononuclear vanadium(Ⅴ) complex with 2-hydroxyl-1-naphthaldehyde isoncotinoyl hydrazone was synthesized and characterized by single-crystal X-ray diffraction.The crystal is of monoclinic,space group P2 1/n with a = 10.3153(15),b = 7.4024(11 ),c = 24.413(4) (A),β= 101.911(2)°,V= 1824.0(5) (A)3,Z = 4,Mr = 427.28,Dc = 1.556 g/cm3,F(000) = 880,μ(MoKα) =0.591,the final R = 0.0372 and wR = 0.0926.The vanadium(Ⅴ) atom adopts a distorted square-pyramidal geometry coordinated by the tridentate ligand and two oxygen atoms.The hydrogen bonds and strong π…π stacking interactions link the complex molecules into a 3-D network structure.     

一种新型稀土配合物Eu(TTA)2(N-HPA)Phen的发光特性研究

合成了一种新的含有3个配体的稀土配合物Eu（TTA）2（N-HPA）Phen（TTA-噻吩甲酰基三氟丙酮，N—HPA=N-苯基邻氨基苯甲酸，phen=邻菲咯啉）。将稀土配合物作为掺杂物与基质PVK按照不同质量比混合共溶，旋涂成膜。通过荧光光谱，分析了薄膜的发光特性，并将其应用于有机电致发光。研究了PVK和Eu（TTA）2（N—HPA）Phen之间的能量传递，并且制备了发光层为PVK：Eu（TTA）2（N—HPA）Phen，结构为ITO／PVK：Eu（TrA）2（N—HPA）Phen／BCP／Alq3／Al的多层器件，发现改变PVK和稀土配合物的掺杂比，可以不同程度地抑制PVK的发光，最终得到纯的Eu^3＋的红色发光。实验结果证明，在PVK：Eu（TTA）2（N—HPA）Phen=5：1的质量比下，从PVK到稀土配合物之间存在充分的能量传递。     

A new Co(II) complex with N,O-donor Schiff base: Synthesis, structure and characterization

A new Co(II) complex with tridentate Schiff base ligand with a N,N,O donor set has been synthesized and characterized by single X-ray technique and spectroscopic techniques. The thermochemical properties have been studied. X-ray structure analysis of the title compound Co(II)L₂ [HL = 2-methyl-6-(2′-hydroxybenzylideneamino) pyridine] shows that the polyhedron around Co(II) is a distorted tetrahedron, and the self-assembly via intermolecular π-π interactions leads to a three-dimensional network. Crystal data for the title complex C₂₆H₂₂CoN₄O₂: Monoclinic, space group Ia, a = 11.741(7) Å, b = 8.149(5) Å, c = 22.764(16) Å, β = 98.530(12)°, V = 2154(2) ų, Z = 4.     

ESR study of NiIII complexes with nitrosonaphthols and dithio acids

Mixed-ligand Ni^III complexes with -nitroso--naphthol, -nitroso--naphthol,o-ethylxanthate, andN,N-diethyldithiocarbamate as ligands have been studied by ESR in liquid and frozen solutions. The degrees of symmetry distortion for the first coordination sphere of these complexes have been determined. It is shown that the transition from planar square Ni^IIL₂ complexes to more stable octahedral Ni^IIIL₂L and Ni^IIILL₂ complexes occursvia the radical addition mechanism. A method for trapping short-lived radicals is suggested on the basis of the complex formation scheme.Translted fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1513–1515, August, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5050)