Binding of Gold(III) from Solutions by Tetranuclear Lead(II) Dipropyldithiocarbamate [Pb4{S2CN(C3H7)2}8] and Chemisorption Synthesis of the Double Ionic Polymer Complex ([Au{S2CN(C3H7)2}2][PbCl3] · 0.5CH3–C6H5)n: Heteronuclear ( 13 C, 15 N) CP-MAS NMR,Structural Organization,and Construction Principles of Cationic and Anionic Polymer Chains

Russian Journal of Coordination Chemistry - Solid-state 13C and 15N CP-MAS NMR data adequately reflected the presence of four nonequivalent PrDtc ligands in the tetranuclear lead(II)...     

Chemisorption of the [AuCl4]− anion by cadmium cyclo-pentamethylenedithiocarbamate and the resulting bound-gold(III) species: The supramolecular structure and thermal behavior of the polynuclear complexes ([Au{S2CN(CH2)5}2]2[CdCl4]) n and ([Au{S2CN(CH2)5}Cl2]) n

The interaction between cadmium cyclo-pentamethylenedithiocarbamate (chemisorbent Ia) and the [AuCl₄]^? anion in 2 M HCl has been investigated. The state of the chemisorbent in contact with AuCl₃ solutions has been probed by ¹¹³Cd MAS NMR spectroscopy. The heterogeneous reactions in the system, including gold(III) chemisorption from the solution and partial ion exchange, yield the gold(III)-cadmium heteropolynuclear complex ([Au{S₂CN(CH₂)₅}₂]₂[CdCl₄]) _n (I) and the polynuclear mixed-ligand complex ([Au{S₂CN(CH₂)₅}Cl₂]) _n (II). The crystal and molecular structures of these compounds have been determined by X-ray crystallography. The main structural units of the compounds are the complex cation [Au{S₂CN(CH₂)₅}₂]⁺, [CdCl₄]^2? anion (in I), and Au{S₂CN(CH₂)₅}Cl₂ molecule (in II). The further structural self-organization of the complexes at the supramolecular level is due to secondary Au...S and Au...Au bonds. [Au₂{S₂CN(CH₂)₅}₄]²⁺ dinuclear cations form in the structure of I, which then polymerize into ([Au₂{S₂CN(CH₂)₅}₄]²⁺) _n chains. In the structure of II, adjacent Au{S₂CN(CH₂)₅}Cl₂ molecules join by forming pairs of asymmetric secondary Au...S bonds, producing polymer chains with alternating antiparallel monomer units. The chemisorption capacity values calculated for cadmium cyclo-pentamethylenedithiocarbamate from gold(III) binding reactions are 455 and 910 mg of gold per gram of sorbent. The gold recovery conditions have been determined by investigating the thermal behavior of I and II by synchronous thermal analysis. The multistep thermal destruction of ionic complex I includes the thermolysis of its carbamate moiety and [CdCl₄]_2? (which liberates gold metal and cadmium chloride and yield some amount of CdS) and CdCl₂ and CdS evaporation. The thermolysis of II proceeds via the formation of Au₂S and AuCl as intermediate compounds. In both cases, the ultimate pyrolysis product is elemental gold.     

A fixation mode of gold(III) in the [Zn2{S2CN(iso-C3H7)2}4]-[AuCl4]−/2 M HCl chemisorption system: Supramolecular structure and thermal behavior of the heteropolynuclear complex ([H3O][Au3{S2CN(iso-C3H7)2}6][ZnCl4]2 · H2O) n

The interaction of freshly precipitated binuclear zinc dithiocarbamate [Zn₂{S₂CN(iso-C₃H₇)₂}₄] with solutions of AuCl₃ in 2 M HCl is studied. The heterogeneous reaction includes the chemisorption of gold(III) and the partial ion exchange to form a polynuclear ionic gold(III)-zinc complex. The molecular and supramolecular structures of the individual fixation mode of gold(III), coordination compound (H₃O[Au₃{S₂CN(iso-C₃H₇)₂}₆][ZnCl₄]₂ · H₂O) _n (I), are determined by X-ray diffraction analysis. Compound I includes three complex cations [Au{S₂CN(iso-C₃H₇)₂}₂]⁺, two of which (noncentrosymmetric, A) are structurally nonequivalent with respect to the third cation (centrosymmetric, B). The structural self-organization of compound I includes the formation of linear trinuclear fragments [Au₃{S₂CN(iso-C₃H₇)₂}₆]³⁺ by three cations (2A and B) due to nonsymmetric secondary Au…S bonds. The interaction between the [Au₃{S₂CN(iso-C₃H₇)₂}₆]³⁺ fragments results in the formation of zigzag polymer chains ([Au₃{S₂CN(iso-C₃H₇)₂}₆]³⁺) _n . The outer-sphere water molecule and the hydronium ion are involved in the pairwise linkage of the [ZnCl₄]₂-anions due to hydrogen bonds Cl…O. The chemisorption capacity of the zinc dithiocarbamate complex calculated from the reaction of gold(III) fixation is 471.2 mg of gold per 1 g of the sorbent. The conditions for the isolation of chemisorbed gold are determined by the simultaneous thermal analysis of the thermal behavior of compound I. The multistage thermal destruction includes two steps of dehydration of the complex, the thermolysis of the dithiocarbamate moiety and [ZnCl₄]^2? (with the release of metallic gold and zinc chloride and the partial formation of ZnS), and the evaporation of ZnCl₂. The final products of the thermal transformations are metallic gold and ZnS.     

Gold(III) preconcentration from acid solutions by cadmium diisopropyldithiocarbamate: Gold(III)-binding species, supramolecular structure, and thermal properties of the heteropolynuclear complex ([Au{S2CN(iso-C3H7)2}2]2[CdCl4] · 1/2C3H6O) n

The reaction of binuclear cadmium diisopropyldithiocarbamate with a solution of AuCl₃ in 2 M HCl was studied. The heterogeneous reaction of gold(III) binding follows a chemisorption scenario (in combination with partial ion exchange) and yields a heteropolynuclear gold(III)-cadmium complex. The molecular and crystal structure of a solvated species of the compound, namely ([Au{S₂CN(iso-C₃H₇)₂}₂]₂[CdCl₄] · 1/2C₃H₆O) _n (I), was solved by X-ray crystallography. The structure of complex I contains (in the ratio 1: 1) structurally nonequivalent molecular cations [Au{S₂CN(iso-C₃H₇)₂}₂]⁺; the differences between these cations allow them to be classified as conformational isomers (cations A and B). The specifics of the supramolecular organization of complex I consist of the alternation of layers of [Au₂{S₂CN(iso-C₃H₇)₂}₄]²⁺ binuclear cations (formed by cations A), ([Au{S₂CN(iso-C₃H₇)₂}₂]⁺) _n polymer chains (formed by cations B), and [CdCl₄]^2? anions. The chemisorption capacity of the precursor cadmium diisopropyldithiocarbamate as calculated from the gold(III) binding reaction is 423.5 mg Au³⁺ per gram of sorbent. The thermal properties of complex I were studied by simultaneous thermal analysis (STA) in order for the parameters of sorbed gold recovery to be determined. The multistep thermal destruction process involves desorption of solvating acetone molecules, thermolysis of the dithiocarbamate part of the complex and [CdCl₄]^2? with release of metallic gold and cadmium chloride and formation of CdS, as well as vaporization of CdCl₂ and CdS. The only final product of thermal conversions is reduced metallic gold.     

[(C2H5)4N]2{Fe4S4[S2CN(C2H5)2]4}的晶体和分子结构

[(C2H5)4N]2{Fe4S4[S2CN(C2H5)2]4}单晶样品在Nicolet-R3四圆衍射仪上收集X射线衍射数据. 分析结果给出其晶胞参数: a=22.125(6), b=11.313(3),c=25.053A; β=118.05(2)°; V=5534.19A^3, Z=4, 空间群Cc. 衍射数据经过Lρ因子和经验吸收效应校正. 分子中铁原子的位置从三维Patterson图上得到. 接着经过若干轮Fourier和差Fourier电子云密度合成, 发现全部其余非氢原子的坐标.氢原子位置根据理论模型计算. 结构修正最后收敛至R=0.073, Rw=0.069. 标题化合物是由[(C2H5)4N]^+和{FeS4[S2CN(C2H5)2]}^2^-组成的离子型化合物. 结构的主要特点表现在阴离子上, 而在阴离子中含有类立方烷型簇核Fe4S4. 该簇核中每个铁原子与五个硫原子配位, 其配位多面体构型均为畸变的四方锥.     

Double Pseudo-Polymeric Gold(III)-Mercury(II) Complexes [Au(S2CNR2)2]nX [R2 = (CH2)6, (CH2)4O] Containing ([HgCl3]−)n, [HgCl4]2− and [Hg2Cl6]2− Anions: Chemisorption Synthesis,Principles of Supramolecular Self-Assembly,and Thermal Behavior

Russian Journal of General Chemistry - Novel pseudo-polymeric complexes of gold(III)-mercury(II) with cyclic alkylene dithiocarbamate ligands: ([Au{S2CN(CH2)6}2][HgCl3])n,...     

Synthesis,Molecular Structure,and Thermal Properties of the Supramolecular Complex [Zn{NH(CH2)4O}{S2CN(C2H5)2}2]2 · CH2N(CH2)4O}2

The supramolecular complex [Zn{NH(CH₂)₄O}{S₂CN(C₂H₅)₂}₂]₂ · CH₂N(CH₂)₄O}₂ (I) has been synthesized and studied by X-ray crystallography and thermal analysis. The noncentrosymmetric complex is composed of two structurally nonequivalent molecules of the adduct of bis(diethyldithiocarbamato)zinc with morpholine, which are linked with the outer-sphere N,N’-dimorpholinomethane molecule through two hydrogen bonds N-H?O. The major differences between the adduct molecules are related to the strength of Zn-N bonds, spatial orientation of the coordinated morpholine heterocyclic rings, and the proportion between the contributions of the trigonal bipyramidal (TBP) and tetragonal pyramidal (TP) components to the geometry of zinc polyhedra. Calculations show that the geometry of the zinc polyhedra is almost halfway between TBP and TP. The thermal destruction of supramolecular compound I is accompanied by desorption of the outer-sphere and coordinated organic molecules. At the final stage, defragmentation of the “dithiocarbamate part” of the complex leads to the formation of ZnS.     

Bismuth(Ⅲ) Complexes with N,N-Di(2-hydroxylethyl)amino-dithiocarboxylate: Synthesis and Crystal Structure of {Bi[S_2CN(C_2H_4OH)_2]_2[1,10-Phen]_2(NO_3)}·3H_2O and {Bi[S_2CN(C_2H_4OH)_2]_3}_2

Introduction The chemistry of organotin(IV) dithiocarbamate complexes was extensively studied due to their biological activities.1-5 To date, a large number of transition-metal complexes with dithiocarbamate have been synthesized and structurally characterized,6-9 including Ni(S2CNC4H8O)2, Cu(S2CNC4H8)2, Zn(S2CNC4H8O)2 and Fe(S2CNC4H8O)2(DMF). However, the chemistry of main-group metal complexes with dithiocarbamate has been scarcely studied, and few reports have appeared on the s…     

Fixation mode of gold(III) in [Cd{S2CN(CH2)4O}2] n -[AuCl4]−/2 M HCl chemisorption system: Preparation, supramolecular self-organization and thermal behavior of the heteropolynuclear complex ([Au{S2CN(CH2)4O}2]2[CdCl4] · H2O) n

A capability of freshly deposited cadmium complex with cyclic morpholinodithiocarbamate ligand (MfDtc) to bind gold(III) from 2 M HCl solutions was studied. The individual form of bound gold (III) isolated from solution was found to be the hydrated heteropolynuclear complex of ionic type ([Au{S₂CN(CH₂)₄O}₂]₂[CdCl₄] · H₂O) _n (I). Molecular and supramolecular structure of preparatively isolated compound I was established by X-ray diffraction study, the structure includes four (1: 1: 1: 1) structurally nonequivalent centrosymmetric complex cations [Au{S₂CN(CH₂)₄O}₂]⁺ which relate to each other in agreement with appeared structural differences as conformers: A, B, C, and D cations with Au(1), Au(2), Au(3), and Au(4), respectively. At the supramolecular level, the isomeric complex cations undergo structural self-organization to form independent polymeric chains of two types: (-A-C-) _n and (-B-D-) _n on account of pairs of unsymmetrical secondary Au…S bonds (3.463, 3.496, and 3.627, 3.669 Å). Distorted tetrahedral [CdCl₄]^2? anions are located in the space between these chains. The chemisorption capacity of cadmium morpholinodithiocarbamate calculated from gold(III) binding is 450.8 mg Au³⁺ per 1 g of sorbent (i.e., each mononuclear fragment of the chemisorbent complex [Cd{S₂CN(CH₂)₄O}₂] binds one gold atom. The conditions of recovery of bound gold were found in the study of thermal behavior of I by simultaneous thermal analysis (STA). The multistep process of thermal destruction includes complex dehydration, thermolysis of its dithiocarbamate fragment and [CdCl₄]^2? to release gold metal, cadmium chloride, and partially CdS.     

Platinum(II) cyclo-hexamethylenedithiocarbamate complex, [Pt{S2CN(CH2)6}2] and its solvated form, [Pt{S2CN(CH2)6}2] · CHCl3: Crystal and molecular structures, 13C CP/MAS NMR data, and thermal behavior

Platinum(II) cyclo-hexamethylenedithiocarbamate (HmDtc) complex, [Pt{S₂CN(CH₂)₆}₂] (I), and its solvated form, Pt{S₂CN(CH₂)₆}₂] · CHCl₃ (II), are synthesized and characterized by the ¹³C MAS NMR data. The HmDtc ligands in structure I are not equivalent, whereas the solvation of the complex is accompanied by the structural unification of the initially nonequivalent HmDtc ligands. In addition, the spectra are characterized by the ¹³C-¹⁹⁵Pt spin-spin coupling. The noncentrosymmetric molecular structure of compound I determined by X-ray diffraction analysis includes two nonequivalent dithiocarbamate ligands coordinated by the metal in the S,S′-bidentate mode. The central atom forming the [PtS₄] chromophore (intraorbital dsp ²-hybrid state of platinum) shifts from the plane of four sulfur atoms by 0.07 Å in the vertex of the flattened tetragonal pyramid. The seven-membered heterocycles ?N(CH₂)₆ of the HmDtc ligands are oppositely directed in space relative to the [S₄] plane (trans orientation). The thermal behavior of compounds I and II are studied by simultaneous thermal analysis. In both cases, the final product of the multistage thermal destruction of the complexes is reduced metallic platinum.     

Pseudo-Polymeric Mercury(II) Morpholinedithiocarbamate [Hg{S2CN(CH2)4O}2]n: Supramolecular Structure (a Role of Secondary Hg···S Bonds), 13C and 15N CP-MAS NMR Spectra,and Thermal Behavior

Russian Journal of Coordination Chemistry - A new representative of mercury(II) dithiocarbamate complexes, crystalline bis(morpholinedithiocarbamato-S,S')mercury(II) with the...     

配合物3AgNO3·2[C3H7S(CH2)2SC3H7]的晶体结构

本文测定了配合物3AgNO3·2BPrTE的晶体结构, 该晶体属三斜晶系, 空间各为PI,晶胞参数: a=0.8945(1), b=1.2355(2), c=1.3572(5)nm; α=98.69(2)°, β=92.74(2)°, γ=90.45(1)°; V=1.480nm^3; Z=2, 分子中三个Ag原子的配位数均为5, 但它们的配位多面体各不相同, Ag(3)为四方锥体, Ag(2)为三角双锥, Ag(1)则介于两者之间, NO3^-以单齿、不等长双齿和等长双齿两种形式配位于Ag原子。配体BPrTE也具有两种构象, 反式构象具有C1对称性, 并以两种形式和Ag原子配位, 偏转式构象不具有C4对称性, 与Ag原子形成五元螯合环, 分子为三维无限长链结构。     

A STUDY OF THE REDOX CHARACTERISTICS OF THE TERNARY CLATHRATE COMPOUND {MolS2CN(C2H5)2]4} {FeCl4}-{C6H5CH2SSCH2C6H5}

The redox characteristics of the ternary clathrate compound{C6H5CH2SSCH2C6H5}was studied by electrochemical measurement and quantum-chemical calculations.The cyclic voltammogram of this ternary clathrate compound in 0.1M KC1O4-DMF with a platinum electride had 2.pairs of redox peak.Both the electrochemical parameters derived from the voltammogram and the results of EHMO calculations indicate that the pair of redox peak at relatively positive potentials corresponds to the redox reaction of "Fe(Ⅲ)/Fe(Ⅱ) which is irreversible in nature,while the pair of redox peak at more negative potentials corresponds to the redox reaction of Mo(Ⅴ)/ Mo(Ⅱ) which is semi-reversible.The calculations from experiment measurements are fairly agreement with the theoretical calculations.     

Formation of the ionic gold(III) complex [Au3{S2CN(CH2)4O}6][Au2Cl8][AuCl4] in chemisorption systems [M{S2CN(CH2)4O}2] n -[AuCl4]−/2 M HCl (M = Cd, Zn): Supramolecular structure and thermal behavior

The interaction of freshly precipitated cadmium and zinc morpholinedithiocarbamates with solutions of AuCl₃ in 2 M HCl is studied. In both cases, the heterogeneous reactions of gold(III) binding from solutions lead to the formation of the ionic gold(III) complex [Au₃{S₂CN(CH₂)₄O}₆][Au₂Cl₈][AuCl₄] (I), whose molecular and supramolecular structures are determined by X-ray diffraction analysis. Compound I includes centrosymmetric and noncentrosymmetric cations [Au{S₂CN(CH₂)₄O}₂]⁺ in a ratio of 1: 2. According to the manifested structural differences, the complex cations are related as conformers (cations A are Au(1) and cations B are Au(2)). At the supramolecular level, the isomeric cations form linear trinuclear structural fragments [Au₃{S₂CN(CH₂)₄O}₆]³⁺ [A...B...A] due to secondary bonds Au...S of 3.6364 Å. The anionic part of compound I is presented by [AuCl₄]^? and centrosymmetric binuclear [Au₂Cl₈]^2?, whose formation involved secondary bonds Au...Cl of 3.486 and 3.985 Å. The ultimate chemisorption capacity of cadmium and zinc morpholinedithiocarbamates calculated from the binding of gold(III) is 901.7 and 1010.4 mg of Au³⁺ per 1 g of the sorbent, respectively (i.e., each miononuclear fragment of the chemisorption complexes [M{S₂CN(CH₂)₄O}₂] participates in binding of two gold atoms). To establish the conditions for the isolation of bound gold, the thermal properties of compound I are studied by simultaneous thermal analysis. The thermal destruction process includes the thermolysis of the dithiocarbamate part of the complex and anions [AuCl₄]^? and [Au₂Cl₈]^2? with the reduction of gold to the metal, being the only final product of the thermal transformations of compound I.     

Syntheses and structures of chalcogen–molybdenum clusters; [Mo3XSe6{S2P(OEt)2}3]Cl, [Mo3X(SeS)3{S2P(OEt)2}3]I and [Mo3 XSe3{S2P(OEt)2}4(py)] (X=0.65S+0.35Se,py= C5H5N)

The trinuclear Mo cluster [Mo3(3–X)(2–Se2)3{S2P-(OEt)2}3]Cl (X=0.65S+0.35Se) (1) has been synthesised by reacting MoCl3·3H2O with ZnSe and [Me4N][S2P(OEt)2] in an EtOH/HCl medium. Reduction of (1) by Ph3P in the presence of [Me4N]-[S2P(OEt)2] and pyridine gave [Mo3(3–X)(2–Se)3 {S2P(OEt)2}4(py)] (X=0.65S+0.35Se, py=C5H5N) (2). Complex (2) was, in turn, converted into [Mo3(3–X)(2–SeS)3{S2P(OEt)2}3]I (X=0.65S+0.35Se) (3) by treatment with H2S and I2. The structures of complexes (1), (2) and (3) were established by X-ray crystallography.     

From an {Fe4S4}-cluster to {Fe2S2}- and {Fe3S}-carbonyls. Crystal structure of [Fe3S(CO)9]2−

We report the electrochemical and chemical synthesis of the first isolable iron carbonyls obtained directly from an {Fe₄S₄}-cluster and carbon monoxide: the structure of one product of chemical reduction, [Fe₃S(CO)₉]²⁻, had been determined by X-ray crystallography.     

Tris(pyrazolyl)borate half-sandwich complexes of trivalent uranium incorporating the [C8H6{SiiPr3-1,4}2]2− and [C8H4{SiiPr3-1,4}2]2− ligands

The reaction of UI₃ in THF with KTp^Me2 and the subsequent addition of [K₂(C₈H₆{SiⁱPr₃-1,4}₂)] or [K₂(C₈H₄{SiⁱPr₃-1,4}₂)] yields dark red [U(κ³-Tp^Me2)(C₈H₆{SiⁱPr₃-1,4}₂)] 1 and purple [U(κ³-Tp^Me2)(C₈H₄{SiⁱPr₃-1,4}₂)] 2, respectively. The ¹H NMR of 1 at room temperature suggests a rigid structure, whereas 2 is fluxional in solution on the NMR timescale. 1 is unreactive towards CO, CO₂ and MeNC under mild conditions; density functional calculations were used to compare the electronic and steric effects of the Tp^Me2 vs. Cp* ligands in mixed sandwich complexes of the type [U(L)(C₈H₆{SiH₃-1,4}₂)] (L = Cp* or (κ³-Tp^Me2)). On heating at 80 °C, 1 reacts with excess MeNC to yield [U(C₈H₆{SiⁱPr₃-1,4}₂)(κ²-dmpz)₂(η¹-CNMe)] 3. The structures of 1–3 have been determined by single crystal X-ray diffraction.     

(C5H7S2)2[Cu3I5]的合成和晶体结构

我们曾经对二硫代乙酰丙酮和多种金属离子的配合反应进行了系统的研究.在成功合成(C_5H_7S_2)_2[CuBr_3]的基础上,最近我们试图用类似方法合成(C_5H_7S_2)[CuI_3].但对产物晶体的X 射线衍射分析结果却表明,所得到的化合物的分子式为(C_5H_7S_2)_2[Cu_3I_5].[Cu_3I_5]~(2-)是以[CuI_3]配位三角形和两个相邻[CuI_4]配位四面体连接的无限链状配合阴离子形式存在.     

Reactions of trans-[Pt(H2){P(C6H11)3}2] with heterocumulenes. The crystal and molecular structure of trans-[Pt{P(C6H11)3}2(H){OCHC(C6H5)2}]

Trans-PtH₂(PCy₃)₂ (1) reacts with phenylisocyanate (2) and with diphenylketene (3) to yield the formamido complex (4) and the vinyloxo complex (5), respectively. The structure of 5 has been determined by X-ray diffraction.     

（C5H7S2）3[Bi2Cl9）]的合成和晶体结构

标题化合物由ＢｉＣｌ３和乙酰丙酮在ＨＣｌ（气）／Ｃ２Ｈ５ＯＨ溶剂中通入Ｈ２Ｓ气体反应而得。晶体属四方晶系，Ｍｔ＝１１３０．７６，空间群Ｐ４１２１２。晶胞参数ａ＝ｂ＝８．８６７（２），ｃ＝４１．５１１（４）Ａ；Ｖ＝３２６４（１）Ａ＾３，Ｚ＝４，Ｄｃ＝２．３０ｇｃｍ＾－３，μ（ＭｏＫａ）＝１１８．６０７ｃｍ＾－１，Ｆ（０００）＝２１０４．晶结构由重原子法求得。最终偏离因子Ｒ＝０．０７２。晶体由分立的（