(PPh4)2[MoN(N3)3Cl]2; Synthese,IR-Spektrum und Kristallstruktur

(PPh₄)₂[MoN(N₃)₃Cl]₂; Synthesis, IR Spectrum, and Crystal Structure The title compound is formed in the reaction of molybdenum (II) benzoate with trimethylsilyl azide and PPh₄Cl in dichloro methane forming dark red single crystals. A PPh₃Me⊕ salt of the ion [MoN(N₃)₃Cl]₂^2? is obtained from (PPh₃Me)₂MoNCl₄] treated with silver azide in CH₂Cl₂ suspension. The solvent CH₂Cl₂ participates in both reactions as oxidizing agent. (PPh₄)₂[MoN(N₃)₃Cl₂ is characterized by a structural analysis based upon X-ray data: space group P1 , Z = 1, a = 1050.7 pm; b = 1185.4 pm; c = 1190.8 pm; α = 98.90°; β = 106.87°; γ = 103.97° (4505 independent, observed reflexions, R = 0.039). The compound consists of PPh₄⊕ cations and centrosymmetric anions [MoN(N₃)₃Cl₂^2? in which the molybdenum atoms are bridged by the N_α atoms of two azide groups; the resulting Mo? N bond lengths are 208 pm and 260 pm. In trans position to the long Mo? N bond the terminal nitrido ligand is situated, the Mo?N distance of 164 pm corresponds to a triple bond. Two terminal azido ligands and the chloro ligand are filling up the coordination sphere of the molybdenum atoms to a coordination number of six. The i.r. spectrum is reported and assigned.     

Synthese und Kristallstrukturen von (PPh4)2[In(S4)(S6)Cl] und (PPh4)2[In(S4)Cl3]

Synthesis and Crystal Structures of (PPh₄)₂[In(S₄)(S₆)Cl] and (PPh₄)₂[In(S₄)Cl₃] InCl and PPh₄Cl yield (PPh₄)₂[In₂Cl₆] in acetonitrile. This reacts with Na₂S₄ in presence of PPh₄Cl, forming (PPh₄)₂[In(S₄)(S₆)Cl]. Its crystal structure was determined by X-ray diffraction (R = 0.075, 2 282 observed reflexions). It is isotypic with (PPh₄)₂[In(S₄)(S₆)Br] and contains anions with trigonal-bipyramidal coordination of In, Cl occupying an axial position, and the S₄ and S₆ groups being bonded in a chelate manner. The reaction of (PPh₄)₂[In₂Cl₆] and sulfur in acetonitrile yielded (PPh₄)₂[InCl₅] and (PPh₄)₂[In(S₄)Cl₃]. The crystal structure analysis of the latter (R = 0.072, 4 080 reflexions) revealed an anion with distorted trigonal-bipyramidal coordination of In, the S₄ group occupying one axial and one equatorial position; the S₄ group shows positional disorder.     

Synthesis,Structure, and Cyclic Voltammetric Property of Metal String Complex [Ni3(dpa)4(ClO4)(Cl)]·CH2Cl2

The metal string complex [Ni₃(dpa)₄(ClO₄)(Cl)] · CH₂Cl₂ ( 1 ) [dpa = bis(2‐pyridyl)amine] with different axial ligands was synthesized and characterized by elemental analysis, IR, UV/Vis, and fluorescence spectroscopy and TG analysis. The molecular structure was determined by single‐crystal X‐ray analysis and its electrochemical properties were investigated. This metal string complex is the first example with different axial ligands, and in its structure a different structural packing relative to the metal string complex [Ni₃(dpa)₄(Cl)₂] ( 2 ) with two axial chloride ligands is generated. The intense C–H ··· π interactions observed for 1 provide additional stability. The axial mono‐substitution of Cl^– by ClO₄^– in 1 relative to 2 results in one obviously short Ni–Ni distance and a higher stability towards oxidation.     

[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构

氯化钆;甘氨酸;固态配合物;[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构     

[NEt4][CoCl3(PPh3)]的合成和晶体结构

标题化合物是反应体系（ＮＨ４）３ＶＳ４／ＣｏＣ２（ＰＰｈ３）２／ＮＥｔ４Ｃｌ在ＣＨ２ＣＩ２中反应而得到的,单晶Ｘ射线结构分析表明其晶体地立方晶系,化学式为Ｃ２６Ｈ３５ＮＣｌ３ＣｏＰ,空间群为Ｐａ３,Ｍｒ＝５５７．８４,ａ＝１７．８０７（５）,Ａ,Ｖ＝５６４６．４Ａ＾３,Ｚ＝８,Ｄｃ＝１．３１ｇ／ｃｍ＾３,Ｆ（０００）＝２３２８,μ（ＭｏＫａ）＝９．６ｃｍ＾－１,Ｒ＝０．０６２,Ｒｗ＝０．０６７,标     

Crystal Structure,Phase Transition and Ferroelastic Properties of [N(CH3)4]3[As2Cl9]

The crystal structure of [N(CH₃)₄]₃[As₂Cl₉] is determined at 293 K. It crystallizes in trigonal space group P31c: a = 9.2199(8), c = 21.065(3)Å, Z = 2, R₁ = 0.0505, wR₂ = 0.1283. The crystal is built of the discrete bioctahedral [As₂Cl₉]^3— anions and the deformed tetramethylammonium cations. A structural phase transition in [N(CH₃)₄]₃[As₂Cl₉] is detected by the DSC and dilatometric techniques at 146/151 K (on cooling/heating). Dielectric relaxation studies in the frequency range 75 kHz — 5 MHz indicate reorientations of the tetramethylammonium cations within the high temperature phase. Optical observations show the existence of the ferroelastic domain structure below 146 K. The possible mechanism of phase transition is discussed on the basis of the presented results.     

Facile Synthesis and Molecular Structure of [Ni(PPh2NHPh)4]

NiCl₂ · 6 H₂O readily reacts with PPh₂NHPh in the presence of zinc dust to yield the homoleptic nickel(0) tetrakis‐phosphine complex [Ni(PPh₂NHPh)₄] ( 1 ). 1 crystallises triclinic P1 (no. 2), with a = 14.656(1), b = 17.124(2), c = 17.424(1) Å, α = 95.998(1), β = 111.845(1), γ = 111.402(1)°, V = 3630.04(5) ų, Z = 2, R values [I > 2σ(I)]: R1 = 0.0554, all data: wR2 = 0.1720. The nickel atom is coordinated in a distorted tetrahedral fashion by four phosphorus atoms, resembling a compressed tetrahedron along one of the non‐crystallographic S₄ axes.     

三苯基膦：转换硫醇保护的纳米粒子成[Au25(PPh3)10(SR)5Cl2]2+

我们在此报道了一种未曾发现的有趣现象：尽管[Au₂₃(SC₆H₁₁)₁₆]⁻、Au₂₄(SC₂H₄Ph)₂₀ (Ph:苯环)、Au₃₆(TBBT)₂₈ (TBBTH:对叔丁基苯硫酚)、Au₃₈(SC₂H₄Ph)₂₄、混合Au_x(SC₂H₄Ph)_y团簇及3 nm的金纳米粒子有不同的组成、结构、尺寸和保护性硫醇配体,但它们在三苯基膦(PPh₃)作用下,均能统一地经由亚稳的[Au₁₁(PPh₃)₈Cl₂]²⁺最终转化为稳定的双二十面体[Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺ (SR:硫醇配体)。换句话说,三苯基膦是这些硫醇保护的纳米粒子的统一转化器。然而,聚乙烯吡咯烷酮(PVP)/柠檬酸盐(Citrate)保护的金纳米粒子和[Ag₂₅(SPhMe₂)₁₈]⁻ (Me:甲基)在同样的条件下,却不能转化为[Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺或[Ag₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺,暗示了硫醇保护的金纳米粒子具有与三苯基膦反应的独特性能。另外,我们考察了配体对双二十面体[Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺团簇荧光性能的影响。     

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

The binary zirconium and hafnium polyazides [PPh₄]₂[M(N₃)₆] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF₄ by fluoride–azide exchange reactions with Me₃SiN₃ in the presence of two equivalents of [PPh₄][N₃]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N₃)₄], [M(N₃)₅]^? and [M(N₃)₆]^2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.     

Synthesis and Crystal Structure of [Fe(Cp)2]3(Bi2Cl9)·thf

Single crystals of [Fe(Cp)₂]₃(Bi₂Cl₉)·thf were obtained from a thf solution containing ferrocene and BiCl₃. The structure shows disorder at room temperature which disappears upon cooling, coupled with a decrease in symmetry. The title compound crystallizes in the orthorhombic space group P2₁2₁2₁ [a = 1698.64(2), b = 2318.69(3), c = 1085.66(2) pm] with three ferrocenium ions, one nonachlorodibismutate ion and one molecule of thf in the asymmetric unit.     

The Coordination Chemistry of the Ylide Adduct O2CC(PPh3)2; Preparation,Crystal Structures,and Spectroscopic Properties of [Cl3In{O2CC(PPh3)2}], [Cl2Sn{O2CC(PPh3)2}], and [I2In{O2CC(PPh3)2}2]I

The betain like carbodiphosphorane CO₂ adduct O₂CC(PPh₃)₂ ( 1a ) can serve as a ligand versus hard Lewis acids from main group compounds. Thus, reaction of 1a with InCl₃, InI₃ and SnCl₂ in polar solvents leads to the addition compounds [Cl₃In{O₂CC(PPh₃)₂}] ( 2 ), [Cl₂SnO₂CC(PPh₃)₂}] ( 3 ) and the salt like compound [I₂In{O₂CC(PPh₃)₂}₂]I ( 4 ) in good yields. Whereas in the indium compounds 1a acts as a chelating ligand, in the tin compound the molecule coordinates with one oxygen atom only as a monodentate ligand. 4 has a pyramidal structure with a stereochemical active pair of electrons. All compounds could be characterized by X‐ray analyses and the usual spectroscopic methods.