Synthesis and characterization by diffraction and 31P- and 77Se-NMR spectroscopy of [Mo3(μ3-Se)(μ2-Se2)3{N(SePPh2)2}3]Br and [Mo3(μ3-Se)(μ2-Se2)3{Se2P(OCH2CH3)2}3]Br

The new Mo/Se clusters [Mo₃(μ₃-Se)(μ₂-Se₂)₃{N(SePPh₂)₂}₃]Br (1) and [Mo₃(μ₃-Se)(μ₂-Se₂)₃{Se₂P(OCH₂CH₃)₂}₃]Br (2) have been synthesized by the selective substitution of the bromo ligands in the starting material [PPh₄]₂[Mo₃(μ₃-Se)(μ₂-Se₂)₃Br₆] with the selenoorgano bidentate ligands [N(SePPh₂)₂]^– and [Se₂P(OEt)₂]^–. The complexes have been characterized in solution by ³¹P- and ⁷⁷Se-NMR spectroscopy and in the solid state by single crystal X-ray diffraction; the same cation structures are present both in solution and in the solid state. Crystallographic data for 1: [Mo₃(μ₃-Se)(μ₂-Se₂)₃{N(SePPh₂)₂}₃]Br·3 CH₂Cl₂, C₇₂H₆₀BrMo₃N₃P₆Se₁₃·3 CH₂Cl₂, trigonal, space group R₃, a=21.299 (10) Å, c=38.433 (27) Å, V=15 100 (15) ų, T=−120 °C, Z=6; crystallographic data for 2: Mo₃(μ₃-Se)(μ₂-Se₂)₃{Se₂P(OCH₂CH₃)₂}₃]Br, C₁₂H₃₀BrMo₃P₃O₃Se₁₃, monoclinic, space group P2₁/n, a=13.404 (2) Å, b=22.732 (4) Å, c=13.932 (3) Å, β=113.134 (3)°, V=3 903.7(12) ų, T=−120 °C, Z=4. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASphosphine ligands / amine ligands / phosphate ligands / selenium / molybdenum cluster / ⁷⁷Se-NMR spectroscopy     

The synthesis of platinum and palladium cluster compounds with isocyanide or functionalised phosphine ligands. Crystal structures of [Pt5(CO)(μ-CO)5{Ph2PCH2C(O) Ph}4 and [Pt5(μ-CNC6H3Me2-2, 6)3(CNC6H3Me2-2, 6)5 {Ph2PCH2C(O) Ph}2]

The reaction of the ketophosphine ligand Ph₂PCH₂C(O)Ph (P～O) with [PtCl₂(NCMe)₂] and carbon monoxide in THF in the presence of an excess of zinc afforded the 70 electron pentanuclear cluster [Pt₅(CO)(μ-CO)₅(P～O)₄] (1). Reaction of the palladium(0) complex [Pd₂(dba)₃] CHCl₃ (dba = dibenzylideneacetone) with Ph₂PCH₂C(O)R [R = Ph or C₅H₄Fe(C₅H₅)] under SO₂ led to the pentapalladium cluster compounds [Pd₅(μ₃-SO₂)₂ (μ-SO₂)₂ {Ph₂PCH₂C(O)R}₅] (2a,R = Ph;2b,R = C₅H₄Fe(C₅H₅)), Cluster (1) reacts with 2,6-xylyl isocyanide, CNC₆H₃Me₂-2,6 to give a red cluster of formula [Pt₅(μ-CNC₆H₃Me₂-2, 6)₃ (CNC₆H₃Me₂-2, 6)₅ (P～O)₂] (3) and a green complex (4). The corresponding complexes (6) and (7) were also obtained by using PPh₃ instead of P～O. Clusters (2a) and (2b) react with [NEt₃Bz] Cl to give[NEt₃Bz][Pd₃(μ-SO₂)₂ (μ-Cl){Ph₂PCH₂C(O)R}₃](8a,R = Ph;8b,R = C₅H₄Fe(C₅H₅)). The molecular structures of (1) and (3) were determined by single-crystal X-ray diffraction analyses.     

Synthesis and Crystal Structure of K3[HO{VO(O2)2}2]·H2O

The title compound K3[HO{VO(O2)2}2]·H2O has been synthesized and its crystal structure was determined by X-ray diffraction method. The crystal is of monoclinic, space group P21/c with a = 6.7078(3), b = 9.9539(6), c = 15.8182(9)A, β = 93.702(3)0, V = 1053.96(10)A3, Mr = 414.20, Dc = 2.610 g/cm3, Z = 4, λ(MoKα) = 0.71073A, F(000) = 808, μ = 3.014 mm-1, the final R = 0.0173 and wR = 0.0466 for 2178 observed reflections with I > 2σ(I). X-ray diffraction reveals that the coordination polyhedra of V atoms are not chemically equivalent: the V(1) and V(2) polyhedra can be described as pentagonal pyramid and pentagonal bipyramid, respectively.     

Synthesis and Structure of Di(μ-Ophenoxy)-bis{nitrato-2-[2-(hydroxyethylimino)-methyl]-phenoloimidazolecopper}

The crystal structure of di(-O_phenoxy)-bis{nitrato-2-[2-(hydroxyethylimino)-methyl]-phenoloimid-azolecopper} was determined. The crystals are monoclinic: a = 10.222(2) Å, b = 13.810(3) Å, c = 10.620(2) Å, =103.67(3)°, space group P2₁/n, Z = 2, R = 0.050. The copper atom coordinates the singly deprotonated 2-[2-(hydroxyethylimino)-methyl]-phenol molecule, imidazole, and nitrate ion. The coordination polyhedron of the central atom is an extended tetragonal bipyramid with imine and imidazole nitrogen atoms and phenol and alcohol oxygen atoms lying in its base. One axial vertex of the bipyramid is occupied by the oxygen atom of the nitrato group and the other vertex, by phenol oxygen atom of the neighboring complex joined with the initial complex by the symmetry center. Two bridging phenol oxygen atoms unite the complexes into a centrosymmetrical dimer.     

Easy Access to Phosphido-Selenido Clusters. Reaction of [Ru3(CO)12] with Ph2(pyth)PSe {pyth=5-(2-Pyridyl)-2-Thienyl} and Crystal Structure of [Ru3(μ3-Se)(μ-PPh2)(μ-pyth)(CO)6{P(pyth)Ph2}]

The reaction of [Ru₃(CO)₁₂] with Ph₂(pyth)PSe (pyth=5-(2-pyridyl)-2-thienyl) allows to obtain two novel clusters [Ru₃(₃-Se)₂(CO)₇{P(pyth)Ph₂}₂] 1 and [Ru₃(₃-Se)(-PPh₂)(-pyth)(CO)₆{P(pyth)Ph₂}] 2 in satisfactory yields. The first one exhibits the well-known bicapped, open triangular, 50-electron nido-core, whereas 2, whose crystal structure has been determined, shows the rather rare Ru₃Se tetrahedron with the Ph₂P and pyth fragments as side-bridging ligands. Morever cluster 2 belongs to the exiguous family of selenido-phosphido clusters not easily achievable by other routes.     

Bis[tetraruthenium(IV)]-containing polyoxometalates: [{Ru(IV)4O6(H2O)9}2Sb2W20O68(OH)2]4- and [{Ru(IV)4O6(H2O)9}2{Fe(H2O)2}2{β-TeW9O33}2H]-

The reaction of [Sb(2)W(22)O(74)(OH)(2)](12-) and [Fe(4)(H(2)O)(10)(β-TeW(9)O(33))(2)](4-) with (NH(4))(2)[RuCl(6)] in aqueous solution resulted in the novel ruthenium(IV)-containing polyanions [{Ru(IV)(4)O(6)(H(2)O)(9)}(2)Sb(2)W(20)O(68)(OH)(2)](4-) and [{Ru(IV)(4)O(6)(H(2)O)(9)}(2){Fe(H(2)O)(2)}(2){β-TeW(9)O(33)}(2)H](-), exhibiting two cationic, adamantane-like, tetraruthenium(IV) units {Ru(4)O(6)(H(2)O)(9)}(4+) bound to the respective polyanion in an external, highly accessible fashion.     

{Cu[H2NC(CH2OH)3]2}{Pic}2·2H2O的合成与晶体结构

三羟甲基氨基甲烷与苦味酸Pic铜在乙醇水混合液中反应,制得少见的不对称氢键连接的超分子化合物{Cu[H2NC(CH2OH)3]2}{Pic}2·2H2O.晶体属三斜晶系,空间群为P ī,晶胞参数为a = 6.894(1),b = 8.219(1),c = 13.543(3) ', α = 79.290(1),β = 8 3.36(2), γ = 84.590(1)°,化学式为C20H30CuN8O22,V = 746.9(2) '3,Z = 1,Dc = 1.774 g/cm3,F000 = 411,μ = 0.844 mm-1,R = 0.0334,Rw = 0.0863.在配合物的结构单元中, Cu2+位于对称中心,分别与2个四齿配体三羟甲基氨基甲烷中的2个-OH,1个-NH2,三齿配位,呈笼状螯合.而另一个-OH,因配体和中心离子构型的限制,不参与配位.     

Thermodynamic Model for BiPO4(cr) and Bi(OH)3(am) Solubility in the Aqueous Na+–H+–\mathrm{H}_{2}\mathrm{PO}_{4}^{-}–\mathrm{HPO}_{4}^{2-}–\mathrm{PO}_{4}^{3-}–OH−–Cl−–H2O System

Prior to this study no data for the solubility product of BiPO₄(cr) or the complexation constants of Bi with phosphate were available. The solubility of BiPO₄(cr) was studied at 23±2?°C from both the over- and under-saturation directions as functions of a wide range in time (6–309 days), pH values (0–15), and phosphate concentrations (reaching as high as 1.0 mol?kg^?1). HCl or NaOH were used to obtain a range in pH values. Steady state concentrations and equilibrium were reached in <6 days. The data were interpreted using the SIT model. These extensive data provided a solubility product value for BiPO₄(cr) and an upper limit value for the formation of BiPO₄(aq). Because the aqueous system in this study involved relatively high concentrations of chloride, reliable values for the complexation constants of Bi with chloride were required to accurately interpret the solubility data. Therefore as a part of this investigation, existing Bi–Cl data were critically reviewed and used to obtain values of equilibrium constants for various Bi–Cl complexes at zero ionic strength along with the values for various SIT ion interaction parameters. Predictions based on these thermodynamic quantities agreed closely with our experimental data, the chloride concentrations of which ranged as high as 0.7 mol?kg^?1. The study showed that BiPO₄(cr) is stable at pH values <9.0. At pH values >9.0, Bi(OH)₃(am) is the solubility controlling phase. Reliable values for the Bi(OH)₃(am) solubility reactions involving Bi(OH)₃(aq) and $\mathrm{Bi}(\mathrm{OH})_{4}^{-}$ and the formation constants of these aqueous species are also reported.     

Synthesis and characterization of α-{3-[2-hydroxy-3-(N-methyl-N-hydroxy-ethylamino)propoxy]propyl}-ω-butylpolydimethylsiloxanes.

α-{3-[2-hydroxy-3-(N-methyl-N-hydroxyethylamino)propoxy]propyl}-ω-butylpolydimethylsiloxanes Ⅲ with various moleculax weights were prepared by epoxy addition of α-[3-(2,3-epoxy-propoxy)propyl]-ω-butylpolydimethylsiloxanes Ⅱ and Nmethylmonoethanolamine.At each step.the outcome compounds were characterized through FT-IR and NMR spectra,the results showed that each step was successfully carried out and objective products were achieved.     

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…     

Synthesis and Crystal Structure of K_3[HO{VO(O_2)_2}_2]·H_2O

1 INTRODUCTION Though the investigation on chemistry of tran- sition metal-peroxy complexes has been extensively carried out, up to now, only four structures of purely inorganic dimeric peroxovanadates have been deter- mined by single-crystal X-ray meth…     

Synthesis and Molecular and Crystal Structure of K4.5{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}I1.5·3H2O and Cs3{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}·2H2O

Crystal structures of two new compounds containing trigonal tellurium-bridged cluster fragments [Mo₃(₃-Te)(₂-Te₂)₃]⁴⁺ were investigated. Crystal data for K_4.5{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}I_1.5·3H₂O: space group , Z = 4, a = 13.280(1), c = 23.800(3) , V = 3635.0(6) ³, d _calc = 3.432 g/cm³, R ₁ = 0.0335, wR2 = 0.0912 for 1378 I _hkl > 2 _I from 3545 measured I _hkl ; for Cs₃{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}·2H₂O: space group P2 ₁ /n, Z = 2, a= 9.650(2) , b = 22.297(5), c = 27.446(7) , = 94.10(2)°, V = 5890(2) ³, d _calc = 4.273 g/cm ³, R ₁ = 0.0384, wR ₂ = 0.0744 for 957 I _hkl > 2 _I from 3758 measured I _hkl (Enraf-Nonius CAD-4 diffractometer, MoK , graphite monochromator). In both compounds, ionic pairs {[Mo₃Te₇(CN)₆]I}^3– with Te_ax...I^– distances of 3.358-3.676 are formed. In the potassium salt, the {[Mo₃Te₇(CN)₆]I}^3– anion pairs are linked by the additional Te_eqI^– short contacts of 3.460 into two-dimensional corrugated layers perpendicular to the c axis of the unit cell. The structure of the cesium salt is ionic with interstitial H₂O molecules and double-layer closest packing of anions.     

离子型化合物{[Ph2Sn]2[2,6-Py(CO2)2]3H2O}2-[HNEt3]+2 的合成及晶体结构研究

在三乙胺作碱的条件下 ,用三苯基氯化锡和 2 ,6 -吡啶二甲酸以 1∶ 1摩尔比反应 ,合成了离子型有机锡化合物 { [Ph2 Sn]2 [2 ,6 -Py( CO2 ) 2 ]3 H2 O} 2 - [HNEt3 ]+2 。用 X-射线单晶衍射测定了该化合物的晶体结构。化合物为单斜晶系 ,空间群 P2 1 /n,a=1 .70 73( 7) nm,b=1 .74 47( 7) nm,c=2 .4 333( 1 0 ) nm,β=1 0 9.6 94 ( 7)°,Z=4 ,V=6 .82 4 ( 5 ) nm3 ,Dx=1 .2 82 g/cm3 ,μ=0 .793mm- 1 ,F( 0 0 0 ) =2 6 96 ,R1 =0 .0 5 6 3,WR2 =0 .1 5 39。化合物中两个锡原子呈七配位畸变五角双锥构型     

CRYSTAL STRUCTURE OF {Mo_3(μ_3-S)(μ-S)_3 [S_2P(OEt}_2]_4·PhCH_2CN}

<正> Mr=2548.12, Triclinic, P1, a=15.941(5), b=15.957(2),c=20.240(6)A, α=76.41(2),β=83.87(2),γ=74.41(2)°,V=4814.6A3, Z=4, Dc=1.757g.cm-3, Final R=0.053 for 11867 reflections. There are two crystallographically independent M1 type trinuclear Mo cluster molecules with 'loose coordination site', A and B, in an asymmetric unit of the title crystal. They are formulated as {Mo3S4(u-dtp)(dtp)3.PhCH2CN}(dtp=[S2P(OEt)2]-) and have essentially identical cluster molecular configuration, but differ from each other in the conformations for the phenyl rings of the ligands PhCH2CN. The lengths of the Mo-Mo bonds are 2.750(1), 2.753(1),and 2.768(1)A for molecule A and 2.742(1), 2.756(1), and 2.764(1)A for molecule B, while the dihedral angles betweem the phenyl ring and the {Mo3} triangle are 25.0° and 94.9° for A and B respectively.     

Synthesis and structure of bismuth-containing complexes [(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}] 2 + [Ph2Bi2I6]2−,[(Ph4Bi]+[PhBi(C5H5N)I3]−, [Ph4Sb] 4 + [Bi4I16]4−⋅2(CH3)2 C=O, and [Ph4Sb] 3 + [Bi5I18]3−

The reactions of tetraphenylbismuthonium and -stibonium salts Ph₄EX (E = Bi, Sb; X = I, OSO₂ (C₆H₃(CH₃)₂-2,5), OSO₂C₆H₃(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph₄Bi]⁺[PhBi(C₅H₅N)I₃]^-, [(Ph₄BiO)₂S(O){2,5-(CH₃)₂C₆H₃S(O)} [Ph₂Bi₂I₆]^2–, [Ph₄Sb [Bi₄I₁₆]^4-·2(CH₃)²C=O, and [Ph₄Sb] ₃₊ ⁺ [Bi₅I₁₈]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.     

{Cu[H_2NC(CH_2OH)_3]_2}{Pic}_2·H_2O的合成与晶体结构

三羟甲基氨基甲烷与苦味酸(Pic)铜在乙醇水混合液中反应,制得少见的不对称氢键连接的超分子化合物{Cu[H2NC(CH2OH)3]2}{Pic}2?H2O。晶体属三斜晶系,空间群为P ,晶胞参数为a = 6.894(1),b = 8.219(1),c = 13.543(3) ? ?= 79.290(1),?= 8 3.36(2), ?= 84.590(1)埃轿狢20H30CuN8O22,V = 746.9(2) 3,Z = 1,Dc = 1.774 g/cm3,F(000) = 411,?= 0.844 mm-1,R = 0.0334,Rw = 0.0863。在配合物的结构单元中, Cu2+位于对称中心,分别与2个四齿配体(三羟甲基氨基甲烷)中的2个OH,1个NH2,三齿配位,呈笼状螯合。而另一个OH,因配体和中心离子构型的限制,不参与配位。     

钼簇合物反应性能的研究: {Mo3S4[S2P(OEt)2]4H2O}的加硫反应以及产物{Mo3(μ3-S)(μ-S2)3[S2P(OEt2]3I}的晶体结构

由贫硫化合物{Mo_3S_4[S_2P(OEt)_2]_4·H_2O}通过加硫获得了富硫化合物{Mo_3S_7[S_2P(OEt)_2]_3·I}(CH_8C_6H_5).化合物属三斜晶系,空间群PI,晶胞参数为a=10.350(1)A,b=13.931(4)A,c=16.369(3)A,α=103.69(2),β=86.62(1),γ=111.99(2)°,V=2183A~3;z=2,D_c=1.817g·cm~(-3).最终结构偏离因子R为0.042. 簇分子{Mo_3(μ_3-S)(μ-S_2)_3[S_2P(OEt)_2]3·I}属{Mo_3(μ3一Y)(μ-S_2)_3[S_2P(OEt)_2]_3·X}(Y=O,S;X=Cl,I)系列构型.{Mo_3}基本上是一个正三角形,Mo—Mo键长分别为2.721(1),2.724(1),2.725(1)A,Mo的配位多面体为七个硫原子组成的畸变五角双锥,有一个I原子联结着三个(S_2)~(2-)桥基的三个不与Mo共平面的S原子,I—S距离平均为3.169A,比相应的Van der Waals距离(～4.00A)明显地短,显示一定程度的成键作用,簇分子的这一构型是一种较为稳定的结构类型.     

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph₃MeP] ₊ ² [SbI₅]^2? (I), [Ph₃MeP] ₊ ² [Sb₃I₁₂]^3? (II), [Ph₃MeP] ₊ ³ [Sb₃I₁₂]^3? · Me₂C=O (III), and [Ph₃MeP] ₊ ³ [Sb₂I₉]^3? (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI₃ groups is bound to the central Sb atom through two μ₂- and one μ₃ iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.