Complex Compounds of Iron(II) with 2,2'-Bipyridylamine and Boron Cluster Anions [BnHn]2– (n = 10, 12)

Russian Journal of Coordination Chemistry - The complexation of iron(II) with 2,2'-bipyridylamine (BPA) in the presence of boron cluster anions [BnHn]2– (n = 10, 12) in aqueous solutions...     

Hexanuclear Niobium Cluster Complex Anions with Acetato Ligands on Intramolecular Bridging Sites: [Nb6Cli4(OAc)i8Cla6]2– and [Nb6(OAc)i12Cla6]2–

From the reaction of [Nb₆Cl₁₄(H₂O)₄] · 4H₂O with acetic anhydride in the presence of an excess of (nBu₄N)F the novel cluster compounds (nBu₄N)₂[Nb₆Clⁱ₄(OAc)ⁱ₈Cl^a₆] ( 1 ) and (nBu₄N)₂[Nb₆(OAc)ⁱ₁₂Cl^a₆] ( 2 ) (OAc = acetato ligand) are obtained. They are the first examples of hexanuclear niobium cluster compounds with acetato ligands on the inner sites of the metal atom octahedron. The crucial role of the presence of fluoride ions in the synthesis is discussed. Each acetato ligand bridges in a μ₂-η¹-fashion with one O atom an edge of the metal atom octahedron. The monoclinic crystals of 1 consist of discrete (nBu₄N)⁺ cations and [Nb₆Clⁱ₄(OAc)ⁱ₈Cl^a₆]^2– cluster anions. They are oxidized by two electrons with respect to the cluster starting material. Besides the syntheses of 1 and 2 , the structure of 1 and spectral properties of both compounds are reported.     

[(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.     

The synthesis and crystal structure of a copper-sulfur cluster [Cu4(S5)2(C5H5N)4]·S8

The cluster [Cu₄(S₅)₂(C₅H₅N)₄]·S₈ with cage structure has been obtained by reaction of copper powder with sulfur and K₂S _x in pyridine, and its structure was determined by X-ray crystallography. The crystal data for the title compound: triclinic, P (No. 2),Z = 2,a = 11.818(4) Å,b = 13.155(3) Å,c = 14.177(4) Å, = 93.79(2)°, = 96.68(2)°, = 115.76(2)°,V = 1954.52(1) ų. The structure was refined toR = 0.038R _w = 0.053) for 6444 data withI > 3.0(I).Dedicated to Professor Jiaxi Lu on the occasion of his 80th birthday.     

Isomerization [trans-B20H18]2– → [iso-B20H18]2– during silver(I) complexation with triphenylphosphine

The trans–iso isomerization of the dimeric borohydride cluster anion [B₂₀H₁₈]^2– in the course of the silver(I) complexation reaction with triphenylphosphine has been described for the first time. The isomeric complexes [Ag₂(Ph₃P)₆[trans-B₂₀H₁₈]] and [Ag₂(Ph₃P)₆[iso-B₂₀H₁₈]] have been isolated and characterized by physicochemical methods. The structures of the compounds have been determined by X-ray crystallography.     

Reactions of ZrOCl2·8H2O with carboxylic acids and thionyl chloride: crystal and molecular structures of K4[Zr(mal)4]·2H2O and K4[Zr(dipic)3]2·13.5H2O

Reactions of ZrOCl₂·8H₂O in aqueous solution with a carboxylic acid in the presence of K₂CO₃ have been studied as a route to Zr^IV-carboxylates. With malonic acid (HO₂CCH₂CO₂H) (H₂mal) the product has been identified as K₄[Zr(mal)₄]·2H₂O (1) by X-ray crystallography. The individual eight-coordinate zirconium anions contain four bidentate (OO) malonate anions with the metal geometry approximating to a square antiprism with each chelating ligand spanning the two square faces, Zr—O 2.091(3)–2.288(3) Å. The four potassium cations feature irregular coordination spheres of oxygen atoms [from both H₂O and (mal) ligand molecules] with a 7–9 coordination range. With 2,6-dicarboxypicolinicacid (HO₂CC₅NH₃CO₂H) (H₂dipic) the product has been characterised as K₄[Zr(dipic)₃]₂·13.5H₂O (2) following X-ray diffraction studies. The structure consists of two [Zr(dipic)₃]^2- anions, four potassium cations and lattice solvate (H₂O) molecules. Individual anions feature nine-coordinate zirconium in which each dipic ligand is terdentate, being bonded via one N (pyridine) and two O (carboxylate) atoms. The metal geometry approximates to tricapped trigonal prismatic with each nitrogen atom capping a regular face of four oxygen atoms, Zr—O, 2.216(6)–2.261(6) Å; Zr—N, 2.343(8)–2.361(7) Å. The potassium cations show similar environments to those observed in structure (1). Dehydration of ZrOCl₂·8H₂O using SOCl₂ in the presence of an excess of THF effects removal of coordinated H₂O molecules and hydroxy bridging groups to provide the anhydrous bis-adduct ZrCl₄(thf)₂ in good yield (72%).     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

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,...     

The Unprecedented [S4N2O10]2− Anion in the Molecular Gold Complexes [Au2Br2(S4N2O10)2] and [Au2Cl2(S4N2O10)2](S2O5Cl2)

The reaction of hexachlorophosphazene, P₃N₃Cl₆, with SO₃ and the gold halides AuCl₃ and AuBr₃, respectively, leads to the new cyclic anionic tetramer, [S₄N₂O₁₀]²⁻, which is coordinated to Au³⁺ in the dimeric complexes [Au₂X₂(S₄N₂O₁₀)₂] (X=Cl, Br). The [S₄N₂O₁₀]²⁻ anion can be seen as the condensation product of two sulfate anions, [SO₄]²⁻_, and two amidosulfate anions, [NH₂SO₃]⁻.     

Rearrangement of the {Mo6S8}cluster fragment to {Mo4S4} and a New {Mo6S6} Cluster Nucleus: Crystal Structure of K6[Mo4S4(CN)12]·10H2O and (18-Crown-6K)8[Mo6S6(CN)16]·17.5H2O

Two new compounds containing molybdenum thiocyanide cluster anions, K₆[Mo₄S₄(CN)₁₂]·10H₂O (1) and (18-crown-6K)₈[Mo₆S₆(CN)₁₆]·17.5H₂O (2), were synthesized and investigated by X-ray structure analysis. Crystal data: a=11.8430(17), b=11.8430(17), c=35.170(7) , V=4932.8(14) ³, space group I4₁/a, Z=4, d_calc=1.563 g/cm³ for 1; a=28.7513(5), b=18.4190(3), c=20.7586(4) , =118.5982(7)°, V=9651.9(3) ³, space group C2/m, Z=4, d_calc =1.563 g/cm³ for 2. The [Mo₄S₄(CN)₁₂]^6- cluster anion in 1 has an ordinary structure typical of cubane transition metal complexes. In the structure of the [Mo₆S₆(CN)₁₆]^8- anion of 2, two crystallographically independent molybdenum atoms form a Mo₆ metallocluster, represented as two edge-sharing tetrahedra.     

Nickel(II) Phosphane- and N-heterocyclic Carbene Complexes with Tridentate,Dianionic [S,N,O]2– Ligands

Square-planar dinuclear nickel(II) complexes containing [S,N,O]^2– ligands formed by condensation of acetyl acetone or benzoyl acetone with cysteamine were prepared. These dimeric nickel(II) compounds undergo bridge-cleavage reactions with the cage phosphine PTA (PTA = 1,3,5-triaza-7-phosphaadamantane) or in situ generated N-heterocyclic carbenes. The resulting diamagnetic, square planar Ni^II complexes were characterized by spectroscopic methods and X-ray diffraction.     

Boron Cluster Anions [B10X10]2– (X = H,Cl) in Manganese(II) Complexation with 2,2'-Bipyridyl

Russian Journal of Coordination Chemistry - The complexation of manganese(II) with 2,2'-bipyridyl in the presence of the [B10H10]2– and [B10Cl10]2– boron cluster anions has been...     

Oxygen-Bridged Ga2(Et)3(OTeF5)3 and the Weakly Coordinating Anions [Ga(Et)(OTeF5)3]− and [Ga(OTeF5)4]−

Salts of the weakly coordinating anions [Ga(OTeF₅)₄]⁻ as well as [Ga(Et)(OTeF₅)₃]⁻ and the neutral Ga₂(Et)₃(OTeF₅)₃ were synthesized and characterized by spectroscopic methods and single-crystal X-ray diffraction. Ga₂(Et)₃(OTeF₅)₃ was formed by treating GaEt₃ with pentafluoroorthotelluric acid (HOTeF₅) and reacted with PPh₄Cl and CPh₃Cl to [PPh₄][Ga(Et)(OTeF₅)₃] and [CPh₃][Ga(Et)(OTeF₅)₃]. In contrast, Ag[Ga(OTeF₅)₄] was prepared from AgOTeF₅ and GaCl₃ and was used as a versatile starting material for further reactions. Starting with Ag[Ga(OTeF₅)₄] the substrates [PPh₄][Ga(OTeF₅)₄] and [CPh₃][Ga(OTeF₅)₄] were formed from PPh₄Cl and CPh₃Cl.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

[Fe2(μ-SC5H4N)2(NO)4] as a New Potential NO Donor: Synthesis,Structure, and Properties

A new potential donor of nitrogen monoxide, a binuclear iron sulfur nitroso complex, was prepared by exchange reaction of Na₂Fe₂(S₂O₃)₂(NO)₄ with pyridine-2-thiol in the presence of sodium thiosulfate at pH 12. The molecular and crystal structures of [Fe₂(-SC₅H₄N)₂(NO)₄] were studied by X-ray diffraction analysis. The type of iron coordination by pyridine-2-thiol in the presence of a coordinated NO molecule was determined. In vacuum, the structure of the complex is destroyed, which is accompanied by NO evolution, while exposure to UV radiation results in decomposition of the complex and in a release of N₂O.     

Synthesis and Crystal Structure of Copper(I) Chloride π-Complexes with N-Allyl- and N,N'-Diallylpiperazinium Dichlorides: [C3H5NH(CH2)4NH2]Cu2Cl4and [C3H5NH(CH2)4NHC3H5]0.5CuCl2

The crystals of copper(I) π-complexes with N-allyl piperazine derivatives, [C₃H₅NH(CH₂)₄NH₂]Cu₂Cl₄(I) and [C₃H₅NH(CH₂)₄NHC₃H₅]_0.5CuCl₂(II), were prepared by alternating-current electrochemical synthesis. X-ray diffraction study showed that compounds Iand IIcrystallize in the monoclinic system: for I, space group P2₁/a, a= 10.254(4) Å, b= 12.306(4) Å, c= 10.656(4) Å, γ = 98.83(3)°, V= 1329(2) ų, Z= 4, R= 0.0457 for 1334 independent reflections; for II, space group P2₁/n, a= 10.187(2) Å, b= 7.283(2) Å, c= 10.480(3) Å, γ = 100.72(2)°, V= 764.0(6) ų, Z= 4, R= 0.0371 for 1025 independent reflections. The structure of Iis composed of {Cu₂Cl₄(C₇H₁₆N₂)}₂dimers linked by fairly strong (N)H···Cl hydrogen bonds (2.35(4) Å). The structure of IIconsists of centrosymmetrical dimeric Cu₂Cl₄ ^2–anions, whose copper atoms coordinate the allyl groups of different centrosymmetrical organic cations. The dimer–ligand chains are stretched along the [ $ {11} $ 0] direction and are joined by hydrogen contacts (N)H···Cl (2.62(4) Å).     

New Cluster Complexes with Octahedral Cores of Niobium Atoms: Syntheses, Structures, and Properties of [K(18-crown-6)]2[K(18-crown-6)(H2O)2]2[Nb6Cl12(CN)6] · 2CH3CN and [(C6H5)4P]4[Nb6Cl12(NCS)6] · 0.94CH3OH

The syntheses and structures of [K(18-crown-6)]₂[K(18-crown-6)(H₂O)₂]₂[Nb₆Cl₁₂(CN)₆] · 2CH₃CN (1) and [(C₆H₅)₄P]₄[Nb₆Cl₁₂(NCS)₆] · 0.94CH₃OH (2), determined by X-ray single crystal diffraction, are reported. Crystal data: [K(18-crown-6)]₂[K(18-crown-6)(H₂O)₂]₂[Nb₆Cl₁₂(CN)₆] · 2CH₃CN: monoclinic, P2₁/n, a = 17.8240(9), b = 15.9395(8), c = 18.660(1) Å, β = 113.833(2)°, Z = 2; [(C₆H₅)₄P]₄[Nb₆Cl₁₂(NCS)₆] · 0.94CH₃OH: triclinic, $ P\bar{1} $ , a = 14.6239(3), b = 14.6237(5), c = 15.9831(3) Å, α = 113.482(1)°, β = 114.684(1)°, γ = 92.585(1)°, Z = 1. Both complexes contain [Nb₆Cl₁₂ Y ₆]^4? cluster anions with Y = CN and NCS, respectively, on all six cluster exo-positions. They have been prepared via ligand substitution in solution, starting from K₄[Nb₆Cl₁₈], which was synthesized by a high temperature solid state reaction. Structural trends and spectroscopic properties are discussed and compared to related compounds reported previously in the literature.     

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [CrVIOF5]−, [CrVOF5]2−, [CrV2O2F8]2−, and [CrIVF6]2− Anions

Molten mixtures of XeF₆ and Cr^VIOF₄ react by means of F₂ elimination to form [XeF₅][Xe₂F₁₁][Cr^VOF₅] ⋅ 2 Cr^VIOF₄, [XeF₅]₂[Cr^IVF₆] ⋅ 2 Cr^VIOF₄, [Xe₂F₁₁]₂[Cr^IVF₆], and [XeF₅]₂[Cr^V₂O₂F₈], whereas their reactions in anhydrous hydrogen fluoride (aHF) and CFCl₃/aHF yield [XeF₅]₂[Cr^V₂O₂F₈] ⋅ 2 HF and [XeF₅]₂[Cr^V₂O₂F₈] ⋅ 2 XeOF₄. Other than [Xe₂F₁₁][M^VIOF₅] and [XeF₅][M^VI₂O₂F₉] (M=Mo or W), these salts are the only Group 6 oxyfluoro-anions known to stabilize noble-gas cations. Their reaction pathways involve redox transformations that give [XeF₅]⁺ and/or [Xe₂F₁₁]⁺ salts of the known [Cr^VOF₅]²⁻ and [Cr^IVF₆]²⁻ anions, and the novel [Cr^V₂O₂F₈]²⁻ anion. A low-temperature Raman spectroscopic study of an equimolar mixture of solid XeF₆ and CrOF₄ revealed that [Xe₂F₁₁][Cr^VIOF₅] is formed as a reaction intermediate. The salts were structurally characterized by LT single-crystal X-ray diffraction and LT Raman spectroscopy, and provide the first structural characterizations of the [Cr^VOF₅]²⁻ and [Cr^V₂O₂F₈]²⁻ anions, where [Cr^V₂O₂F₈]²⁻ represents a new structural motif among the known oxyfluoro-anions of Group 6. The X-ray structures show that [XeF₅]⁺ and [Xe₂F₁₁]⁺ form ion pairs with their respective anions by means of Xe- - -F–Cr bridges. Quantum-chemical calculations were carried out to obtain the energy-minimized, gas-phase geometries and the vibrational frequencies of the anions and their ion pairs and to aid in the assignments of their Raman spectra.