Two new [Ni(tren)2]2+ complexes: [Ni(tren)2]Cl2 and [Ni(tren)2]WS4

Both title compounds, bis­[tris(2‐amino­ethyl)­amine]­nickel(II) dichloride, [Ni(tren)₂]Cl₂, (I), and bis­[tris(2‐amino­ethyl)­amine]­nickel(II) tetra­thio­tungstate, [Ni(tren)₂]WS₄, (II), contain the [Ni(tren)₂]²⁺ cation [tren is tris(2‐amino­ethyl)­amine, C₆H₁₈N₄]. The tren mol­ecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni²⁺ is located on a centre of inversion surrounded by one crystallographically independent tren mol­ecule. In the [Ni(tren)₂]²⁺ cation of (II), the Ni atom is bound to two crystallographically independent tren mol­ecules. The Ni atoms in the [Ni(tren)₂]²⁺ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren mol­ecules. The counter‐ions are chloride anions in (I) and the tetrahedral [WS₄]^2? anion in (II). Hydro­gen bonding is observed in both compounds.     

Double complex salts [Ni(NH3)6]3[Fe(CN)6]2 and [Ni(NH3)6]3[Cr(CNS)6]2: Synthesis and properties

The double complex salts [Ni(NH₃)₆]₃[Fe(CN)₆]₂ and [Ni(NH₃)₆]₃[Cr(CNS)₆]₂ were synthesized and their thermal decomposition in air was studied. The values of interplanar distances in crystal lattices were determined. The compounds are proposed as precursors for producing homogeneous bimetallic nanodimensional powders.     

The Disproportionation of [Ni(tacn)]2+ in Ni2+ and [Ni(tacn)2]2+ Crystallographically Demonstrated (tacn=1,4,7‐Triazacyclononane)

From an EtOH/H₂O solution, 0.3 M each of Ni²⁺ and cyclic triamine tacn ( 2 ; tacn=1,4,7‐triazacyclononane), after 10 min refluxing and cooling at room temperature, copious and comparable amounts of blue crystals (containing the complex [Ni(tacn)(H₂O)₃]²⁺) and pink crystals (containing in the same cell both [Ni(H₂O)₆]²⁺ and [Ni(tacn)₂]²⁺) precipitated. This unusual behaviour is ascribed to the fact that at the refluxing temperature the three species are present at the equilibrium in similar concentrations, which are frozen on cooling, due to the inertness of the macrocyclic complexes [Ni(tacn)(H₂O)₃]²⁺ and [Ni(tacn)₂]²⁺.     

Towards Single-component Molecular Conductor [Ni（dmit）2 ] by Charge Disproportionation： 2[Ni（dmit）2]^0.5→[Ni（dmit）2 ]＋ [Ni（dmit）2]^-

A new method of synthesizing single-component molecular conductor [Ni(dmit)2] bythe reaction 2(Me4N)[Ni(dmit)2]2→ [Ni(dmit)2] (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2]exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.     

Synthesen und Charakterisierung von [Ni(tBuAs)6] und [Pd(tBuAs)6]

Syntheses and Characterization of [Ni(tBuAs)₆] and [Pd(tBuAs)₆] The reduction of tBuAsCl₂ with magnesium in the presence of NiCl₂ or PdCl₂ yields the complexes [Ni(tBuAs)₆] ( 2 ) and [Pd(tBuAs)₆] ( 3 ). The structure of ( 2 ) was determined by X-ray single crystal structure analysis. ( 2 ) consists of the sixmembered ring (tBuAs)₆ in chair conformation with the nickel atom in the center of this ring.     

[Ni(cien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

硫氰酸根的结构为N三C-S-,其两端的N原子和S原子分别有一对和三对孤对电子,因此,硫氰酸根可采用多种不同的配位模式与金属离子发生配位.硫氰酸根可作为单齿配体与一个金属离子配位,形成M-SCN或M-NCS的单核配合物,也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物[1-3];另一方面,硫氰酸根是一个具有一定共轭性的偶极子,可传递磁相作用.因此,选择硫氰酸根作为桥联配体,将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子,并研究它们的磁性已成为分子磁学的一个研究领域[4-6].本文仅报道标题配合物的合成与晶体结构.     

Synthesen und Kristallstrukturen der chalkogenidoverbrückten Nickelclusterverbindungen [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6] und [Ni18S18(PiPr3)6]

Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni₅Se₄Cl₂(PPhEt₂)₆], [Ni₁₂Se₁₂(PⁿPr₃)₆], and [Ni₁₈S₁₈(PⁱPr₃)₆] The reaction of (R)ESiMe₃ (R = SiMe₃, Mes = C₉H₁₁; E = S, Se) with [NiCl₂(PPhEt₂)₂] and [NiCl₂(PR₃)₂] (R = ⁿPr, ⁱPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni₅Se₄Cl₂(PPhEt₂)₆]·2THF ( 1 ), [Ni₁₂Se₁₂(PⁿPr₃)₆]·2THF ( 2 ), and [Ni₁₈S₁₈(PⁱPr₃)₆]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

Derivate des Flußspat-Typs: [Fe(NH3)6][TaF6]2 und [Ni(NH3)6][TaF6]2

Derivatives of the Fluorite Type: [Fe(NH₃)₆][TaF₆]₂ and [Ni(NH₃)₆][TaF₆]₂ Light blue single crystals of [Fe(NH₃)₆][TaF₆]₂ and [Ni(NH₃)₆][TaF₆]₂ are obtained from 36 : 1 : 6 molar mixtures of (NH₄)F, iron/nickel and tantalum powders, respectively, in sealed Monel metal ampoules at 400 °C. They both crystallize isotypic with [Co(NH₃)₆][PF₆]₂ (cubic, Fm-3m, Z = 4, a = 1259.0(2)/1260.4(2) pm) in a structure that can be derived from the basic fluorite-type of structure according to [Ca][F]₂≡[Fe(NH₃)₆][TaF₆]₂, for example.     

Triplet electronic states in d(2) and d(8) complexes probed by absorption spectroscopy: a CASSCF/CASPT2 analysis of [V(H2O)6]3+ and [Ni(H2O)6]2+

Octahedral complexes of transition metal ions with d(2) and d(8) electron configurations have triplet electronic states with identical T(2g), A(2g), T(1g)((3)F), and T(1g)((3)P) symmetry labels. CASSCF and CASPT2 calculations indicate the predominant electronic configurations for each triplet state. The two (3)T(1g) states show strong configuration mixing in the d(8) complex [Ni(H(2)O)(6)](2+), but much weaker mixing occurs between these states in the d(2) compound [V(H(2)O)(6)](3+). Calculated vibrational frequencies and equilibrium geometries for the triplet states are used to obtain theoretical absorption spectra that are in agreement with the experimental data.     

新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

Towards Single-component Molecular Conductor [Ni(dmit)_2] by Charge Disproportionation:2[Ni(dmit)_2]~(-0.5)[Ni(dmit)_2]+[Ni(dmit)_2]~-

It was commonly thought that a molecular conductor or semiconductor should be composed of at least two components to make the conducting component in partially charged state. However, this idea became questionable by the recent report of the single-component molecular conductor [Ni(tmdt)2]1 as well as several reports about single-component molecular semiconductors such as [Ni(ptdt)2]2 and [Ni(C10H10S8)2]3. In fact, as early as 1985, [Ni(dmit)2] as a by-product in synthesizing TTF[Ni(dmit…