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.     

Synthesis and structure of Mu-4, the new layered aluminophosphate [(C2H5)2NH2]4[Al8P10O40H2]·[H2O]2.5

The title compound (named Mu-4) is a new layered aluminophosphate with a unusual A1/P ratio for this kind of materials. Mu-4 was obtained from a quasi non-aqueous mixture involving mainly diethylformamide (DEF) as solvent, in addition to limited amounts of water. DEF is decomposed during the synthesis and the resulting protonated diethylamine is occluded in the as-synthesized material. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is triclinic, a=8.632(4) Å, b=9.267(7) Å, c= 17.461(10) Å, α=86.66(5)°, β=82.20(4)° and γ=89.28(5)°, space group P-1. The structure consists of anionic double sheets essentially built from double 4-ring (D4R) units. The inorganic layers are in strong interaction with water and the protonated amine which is located in the interlayer spacing. Another type of diethylamine protrudes into the 8-membered rings (8-MR) present in the layers. The characterization of this new aluminophosphate by ¹³C, ²⁷Al and ³¹P solid state NMR spectroscopy is also reported.     

Bi3GaS5]2[Ga3Cl10]2[GaCl4]2·S8 containing heterocubane-type [Bi3GaS5]2+, star-shaped [Ga3Cl10]-, monomeric [GaCl4]- and crown-like S8

By reaction of elemental bismuth, sulfur, bismuth(III) chloride and gallium(III) chloride in the ionic liquid (BMIm)Cl (BMIm: 1-butyl-3-methylimidazolium), [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is obtained as red transparent crystals. According to X-ray structure analysis based on single crystals, the title compound crystallizes with triclinic lattice symmetry and is composed of heterocubane-type [Bi(3)GaS(5)](2+) cations, trimeric star-shaped [Ga(3)Cl(10)](-) anions with three (GaCl(4)) tetrahedra sharing a single central chlorine atom, monomeric [GaCl(4)](-) tetrahedra and neutral, crown-shaped S(8)-rings. Here, the heterocubane [Bi(3)GaS(5)](2+) as well as the star-shaped [Ga(3)Cl(10)](-) are observed as building units for the first time. [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is further characterized by X-ray powder diffraction as well as by thermogravimetry/differential thermal analysis.     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

SYNTHESIS AND CRYSTAL STRUCTURE OF [C8H8NdCl（THF）2]2

<正> The title complex was prepared from the reaction of NdClLi0.3 and C8H8, its crystal structure was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P21/c with cell dimensions o = 11. 819(3), 6=12.651(3), c=13. 478(3)A, β=122.99(2)°, Mr = 856. 00, Z = 2, Dc=1. 68g/cm3, F(000) = 636. 89, V = 1690. 33A3. The structure was solved by direct methods and Fourier techniques. Least squares refinement on the basis of 1842 observed reflections led to final R = 0. 038 and Rw = 0. 040. The molecule is a dimer of C3H8NdCl(THF)2 bridged by two Cl atoms with Nd -Cl bond lengths of 2. 832(2) A and 2. 917(3)A.     

Ti-Verbindungen mit fulvalenbrücken: Die struktur von [CpTiMe2]2(C10H8)

X-ray analysis for the orange-yellow thermally unstable crystalline compound [CpTiMe₂]₂(C₁₀H₈) (3(Me)), which results from methylation of [CpTiCl₂]₂(C₁₀H₈), confirms the presence of a fulvalene bridge. The two CpTiMe₂ fragments in 3(Me) are trans with respect to the fulvalene group.     

Complex [Ag(PPh3)4][2-B10H9NH3 · 2DMF]: Synthesis and Structure

Russian Journal of Coordination Chemistry - The formation of complex salt [Ag(PPh3)4][2-B10H9NH3 ? 2DMF] (I) by the reaction of the salts of the [2-B10H9NH3]– anion with [Ag(PPh3)4]NO3...     

化合物[H3DETA]3[H2DETA]2[Pr(SiW11O39)2]·2H2O的水热合成及晶体结构

通过水热合成制得了硅钨杂多酸镨化合物[H3DETA]3[H2DETA]2[Pr(S iW11O39)2].2H2O[DETA:二乙烯三胺].晶体结构解析表明:该化合物属于三斜晶系,P1-空间群,a=1.200 0(2)nm,b=2.026 1(4)nm,c=2.239 2(5)nm,α=111.60(3)°,β=92.92(3)°,γ=103.56(3)°;V=4.863 8(17)nm3,Z=2,ρ=4.152 g/cm3,μ=26.519 mm-1,F(000)=5 374.化合物中Pr3+键合两个[S iW11O39]8-构成一个[Pr(S iW11O39)2]13-多阴离子,Pr3+与两个[S iW11O39]8-阴离子的八个氧原子配位构成一个畸变的四方反棱柱.此外,多阴离子[Pr(S iW11O39)2]13-和有机分子还通过氢键形成一个大的空腔.     

Synthesis,Structure and Properties of a Novel Copper（II）-2,2- biimidazole Complex-supported Compound： [Cu（H2biim）2] { [Cu（H2biim）2]2 [H10W12O44] }.8H2O

A new copper（II）-2,2＇-biimidazole metal-organic POMs-supported compound [Cu（H2biim）2]{[Cu（H2biim）212[H10W12O44]}＇8H2O （H2biim = 2,2＇-biimidazole） has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800（2）, b = 13.437（3）, c = 13.685（3） A, V = 1922.5（7） A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F（000） = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections （I 〉 2σ（I））. X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu（H2biim）2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.＇-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.     

[2,6(9)-B10H8>(O)2CCH3]− and [2,7(8)-B10H8(OC(O)CH3)2]2− derivatives in synthesis of position isomers of the [B10H8(OC(O)CH3)(OH)]2− anion with the 2,6(9)- and 2,7(8)-arrangement of functional groups

The interaction of Cat₂B₁₀H₁₀ (Cat = Ph₄P⁺, Ph₄As⁺) with acetic acid has been studied. Disubstituted closo-decaborate derivatives with a bidentately bound acetate group, Cat[2,6(9)-B₁₀H₈>(O)₂CCH₃], or two monodentate acetate groups, Cat₂[2,7(8)-B₁₀H₈(OC(O)CH₃)₂], have been isolated (Cat = Ph₄P⁺, Ph₄As⁺). Hydrolysis of these compounds has led to the position isomers of the [B₁₀H₈(OC(O)CH₃)(OH)]^2? anion with the hydroxo and acetate groups in the 2,6(9)- and 2,7(8)-positions. The structures of {Pb(Bipy)₂[2,6(9)-B₁₀H₈(OC(O)CH₃)(OH)]}₂ · 3H₂O, (Ph₄As)₂[2,6(9)-B₁₀H₈(OC(O)CH₃)(OH)] · 0.4C₂H₅OH · 0.25H₂O, and (Ph₄As)₂[2,7(8)-B₁₀H₈(OC(O)CH₃)(OH)], as well as of the product of the reaction of the B₁₀H ₁₀ ^2? anion with formic acid (Ph₄P)₂[2-B₁₀H₉OC(O)H] · CH₃CN, have been determined by X-ray crystallography.     

Synthesis and structure of antimony complexes [Ph3AmP] 2 + [Sb2I8 · 2DMSO]2−, [Ph3PrP] 2 + [Sb2I8 · C4H8O2]2−, and [(HOCH2CH2)3NH] 4 + [Sb4I16]4−

The reaction of equimolar amounts of triphenylamyl- and triphenylpropylphosphonium iodides and triethanolammonium iodide with antimony iodide in dimethyl sulfoxide, dioxane, or acetone gave complexes [Ph₃AmP] ₂ ⁺ [Sb₂I₈ · 2DMSO]^2?, [Ph₃PrP] ₂ ⁺ [Sb₂I₈ · C₄H₈O₂]^2?, and [(HOCH₂CH₂)₃NH] ₄ ⁺ [Sb₄I₁₆]^4?, the structure of which was established by X-ray diffraction analysis. The cations of all complexes have slightly distorted tetrahedral structure, and the antimony atoms in the anions are hexacoordinated. The crystals of the complexes have intra- and intermolecular contacts, which form the structure.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Photolysis of [PtBr6]2– complex in frozen methanol matrix

Photochemistry of the [PtBr₆]^2– complex in the low-temperature methanol matrix (77 K) was studied by low-temperature spectrophotometry and ESR spectroscopy. The [PtBr₄]^2– complex is the main photolysis product. The mechanism of two-electron reduction of the platinum(IV) ion is proposed. The primary photochemical process is electron transfer from the solvent molecule to the photoexcited initial complex to form the intermediate radical complex ([PtBr₆]^3–...^·CH₂OH). The transfer of the second electron in the radical complex produces the final reaction products.     

(NH4)2[Cu(C10H8N2)2Mo8O26]的水热合成及晶体结构

采用水热反应合成了一个无机-有机杂化的β-{Mo8O26}簇合物(NH4)2[CU(C10H8N2)2Mo8O26并通过X-射线单晶衍射对其结构进行了分析.该化合物为三斜晶系P(i)空间群,晶胞参数为a=0.76757(2)nm,b＝1.07870(2)nm,c=1.28795(2)nm,α=100.6150(10)°...     

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H2O)6]H3[V10O28] · 2H2O: Synthesis and study

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H₂O)₆]H₃[V₁₀O₂₈] · 2H₂O (I) was obtained and examined by mass spectrometry, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The crystals are monoclinic, space group $P\bar 1$ a = 7.862(3), b = 8.427(5), c = 5.000(2) Å, β = 96.46(4)°, V = 867.0(3) ų, ρ_calcd = 5.83 g/cm³, Z = 1.     

Intramolecular [8+2] cycloaddition and 10π-electron electrocyclization reactions of an 8-acylheptafulvene

Compound 8-(trans-3-ethoxycarbonylallylacetyl)heptafulvene,8, undergoes both an intramolecular [8+2] cycloaddition and a 10π-electron electrocyclization followed by 1,5-sigmatropic hydrogen shifts to give10 and₁₂, respectively.     

STRUCTURE OF [Et4N]2[Mo2（CO）8（SCH2C6H4CH2SH）]

<正> Mr =1015.05, P21/c, a= 10.912(4), b= 12.088(3), c= 18.807(8) A.β=103.57(3)° ,V= 2411.4 A3, Z = 2, DC = 1.40 g/cm3.λ(MoKα)= 0.71073 A, μ=7.2 cm-1,F(000)=1048.Room temperature, final R=0.069, Rw=0.091. The geometry around the Mo atom is a distorted octahedron. The equatorial Mo-C distances are shorter than the axial ones. The Mo...Mo distance is 3.949A.     

Cleavage of the cyclic substituent in the [B10H9O2C4H8]−, [B10H9OC4H8]−, and [B10H9OC5H10]− anions upon the interaction with negatively charged N-nucleophiles

The interaction of the [B₁₀H₉O₂C₄H₈]^?, [B₁₀H₉OC₄H₈]^?, and [B₁₀H₉OC₅H₁₀]^? anions with negatively charged N-nucleophiles has been studied. It has been shown that such reactions yield doubly charged substituted closo-decaborates with a nitrogen-containing group attached to the cluster through an alkoxyl spacer. Compounds with pendant NO₂ ^?, N₃ ^?, N(CO)₂C₆H₄ ^?, and NHC₆H₅ groups have been synthesized.     

SYNTHESIS OF 15H-ISOQUINO[2′,3′:3,4]IMIDAZO[2,1-B]QUINAZOLINE-7,13,15-TRIONES AND 14H-ISOQUINO[2′,3′:3,4]IMIDAZO[2,1-B]BENZO[G]QUINAZOLINE-8,14,16-TRIONE AS NEW POLYCYCLIC FUSED-RING SYSTEMS

3-Thioxo-2H-imidazo[1,5-b]isoquinoline-1,5-dione (3) and 2-sub-stituted 3-thioxo-2H-imidazo[1,5-b]isoquinoline-1,5-diones (4a–l) were prepared from the reaction of 2-thiohydantoin (2) and 3-substituted 2-thiohydantoin (5a–l) with 2-formyl benzoic acid (1). Alkylation of 3 under an anhydrous basic conditions afforded 4a–i. The alkylation of 3 in aqueous basic solution afforded 3-(alkylmercapto)imidazo[1,5-b]isoquinoline-1,5-diones (7a,b). Reactions of the aromatic amino acids 9a,b and 12 with 7a afforded 2-(2H-1,5 dioxoimidazo[1,5-b]isoquinazolin-3-ylideneamino)benzoic acids (10a, b) and 3-(2H-1,5-dioxoimidazo[1,5-b]isoquinazolin-3-ylideneamino)2-naphthalenecarboxylic acid (13), which were then cyclyzed by heating in acetic anhydride to afford 15H-isoquino[2′,3′ :3,4] imidazo[2,1-b]quinazoline-7,13,15-triones (11a,b) and 14H-isoquino[2′,3′:3,4]imidazo[2,1-b]benzo[g]quinazoline-8,14,16-trione (14). Some of the new compounds were tested for their antitumor activities.