Cluster Complexes of Polythioether Macrocycles: The Synthesis and Molecular Structures of Ru6(CO)13(cis-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C) and Ru6(CO)13(trans-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C)

The reaction of a mixture of cis-3,7,11-trimethyl-1,5,9-trithiacyclododecane, cis-Me₃12S3, 1 and trans-3,7,11-trimethyl-l,5,9-trithiacyclododecane, trans-Me₃12S3, 2, with Ru₆(CO)₁₇(μ ₆-C), 3, yielded three new cluster compounds Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 4, and two isomers of Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 5a and 5b. The molecular structures of 4 and 5b were established by single crystal X-ray diffraction analyses. In both complexes, the macrocycles have adopted tridentate coordination with one of the sulfur atoms in a bridging position. Two carbonyl ligands occupy bridging positions in each compound. Crystal Data for 4·Me₂CO: space group=P2₁/n, a=11.295(1) Å, b=17.547(3) Å, c=20.318(3) Å, β=93.71(1)°, Z=4, 2900 reflections, R=0.025. Crystal Data for 5b·1.5 C₆H₆: space group=Pbca, a=31.8900(8) Å, b=23.4330(6) Å, c=21.6240(4) Å, Z=16, 12163 reflections, R=0.040.     

Cyclohexylamine) 2 M(CN) 4 ⋅2C 6 H 6 (M = Cd or Hg)

Two new title compounds have been prepared in powder form. Their spectral data are found to be consistent with the structure foundin Hofmann-T_d-type clathrates.     

(CH2 )2 (C9 H6 )2 YbN(SiMe3 )2 的合成与催化活性研究

用1,2-二茚基乙烷[(CH2)2(C9H7)2]与四配位的三[三甲基硅基胺基]镱的络合物{[(Me3Si)2N]3Yb(Ⅲ)(μ-Cl)Li(THF),}反应,生成桥联二茚基镱的胺基配合物[(CH2)2(C9H6)2YbN(SiMe3)2],其结构经^1HNMR,IR,XFD),GPC和元素分析表征,并初步研究了其对甲基丙烯酸甲酯聚合反应的催化活性。     

Crystal Growth and Crystal Structures of Gold(V) Compounds: Cu(AuF6)2, Ag(AuF6)2, and O2(CuF)3(AuF6)4 ⋅ HF

Crystal growth from anhydrous hydrogen fluoride solutions of M²⁺ (M=Cu, Ag) and [AuF₆]⁻ gave M(AuF₆)₂ salts (M=Cu, Ag). Similar attempts to prepare single crystals of the corresponding nickel, zinc and magnesium salts failed. The crystal structure of Cu(AuF₆)₂ consists of layers of Cu²⁺ cations connected by [AuF₆]⁻ anions, thus forming slabs. Only van der Waals interactions exist between adjacent slabs. The crystal structure of Ag(AuF₆)₂ consists of a three-dimensional framework in which Ag⁺ cations are linked by [AuF₆]⁻ anions. Both structures are members of the M^II(X^VF₆)₂ family, in which seven different structure types have been observed to date. In the crystal structure of O₂(CuF)₃(AuF₆)₄ ⋅ HF, the bridging AuF₆ units connect [−Cu−F−Cu−F−]_∞ chains to form stacks between which O₂⁺ cations and HF molecules are located.     

Syntheses, X-ray structural characterizations, and thermal stabilities of two nonclassical trinuclear vanadium(IV) complexes, (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(H2O) and (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(py), and polymeric complexes of stoichiometry (VO(O2PR2)2)∞, R2 = Ph2 and o-(CH2)2(C6H4)

The preparation and structural characterization of two trinuclear vanadium complexes, (V(3)(μ(3)-O)O(2))(μ(2)-O(2)P(CH(2)C(6)H(5))(2))(6)(H(2)O), 1, and (V(3)(μ(3)-O)O(2))(μ(2)-O(2)P(CH(2)C(6)H(5))(2))(6)(py), 2, are reported. In these nonclassical structures, the planar central core consists of the three vanadium atoms arranged in the form of an acute quasi-isosceles triangle with the central oxygen atom multiply bonded to the vanadium atom at the center of the vertex angle and weakly interacting with the two other vanadium atoms on the base sites, each of which contain one external multiply bonded oxygen atom. Reacting VO(acac)(2)in the presence of diphenylphosphinic acid affords (VO(O(2)PPh(2))(2))(∞), 3, while 2-hydroxyisophosphindoline-2-oxide at room temperature in CH(2)Cl(2) affords ((H(2)O)VO(O(2)Po-(CH(2))(2)C(6)H(4))(2))(∞), 4, and at 120 °C in EtOH yields (VO(O(2)P(o-(CH(2))(2)(C(6)H(4)))(∞), 5 on the basis of elemental analyses. The thermal and chemical stability of the complexes were assessed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements. The bond strengths of the vanadium atoms to the OH(2) ligand in 1 and to the NC(5)H(5) ligand in 2 were assessed at 10.7 and 42.0 kJ/mol respectively. Room temperature magnetic susceptibility measurements reveal magnetic moments for trinuclear 1 and 2 at 3.02(1) and 3.05(1) μ(B/mol), and also close to spin only values (1.73 μ(B)) values for 3, 4, and 5 at 1.77(2), 1.758(7), and 1.77(3) μ(B), respectively. Variable-temperature, solid-state magnetic susceptibility measurements were conducted on complex 2 in the temperature range of 2.0-298 K and at an applied field of 0.5 T. Magnetization measurements at 2 and 4 K confirmed a very weak magnetic interaction between the vanadyl centers.     

有机锡配合物[(o-Cl-PhCH2)2Sn(OCOC9H6N)2]·2(C6H6)的合成和晶体结构研究

0引言某些有机锡羧酸酯化合物具有杀虫、杀菌和抗癌活性,引起人们极大的兴趣[1~3]。近年来的研究结果表明,该类化合物中心锡原子的配位形式既决定于与锡原子直接相连的烃基的结构,也与配体的类型有关,尤其是含有孤电子对的杂环酸的引入,导致了许多新型结构有机锡化合物的产生[4     

Synthesis, structure and reactivity of binuclear metal-metal bonded molybdenum(V) and tungsten(V) thioselenohalides: Molecular structure of Mo2(μ-S2)2Cl6(SeCl2)2 and W2(μ-S2)2Cl6(SeCl2)2

Thioselenohalide complexes Mo₂(μ-S₂)₂Cl₆(SeCl₂)₂ (I), Mo₂(μ-S₂)₂Br₆(SeBr₂)₂ (II), and W₂(μ-S₂)₂Br₆(SeBr₂)₂ (III) were synthesized by the reactions of corresponding metal halides or carbonyls or molybdenum metal with excesses of S₂ X ₂+Se₂ X ₂ mixtures. The complex W₂(μ-S₂)₂Cl₆(SeCl₂)₂ (IV) was obtained by an exchange reaction between (III) and excess of Se₂Cl₂. Coordination of the neutral SeX ₂ ligands to thiohalidesM ₂(μ-S₂)₂ X ₆ results in higher thermal stability, and suggests the possibility to synthesize SeX ₂ complexes of the unstable parent tungsten thiohalides. An unusual oxidative addition reaction of (I) was detected: {fx27-1} Both (I) and (IV) were characterized by X-ray crystal structure analysis. They are isostructural and form discrete molecules. Bridging S ₂ ^2? ligands are coordinated perpendicularly to the metal-metal bond;d(M?M)=2.8066 Å and 2.793 Å for I and IV, respectively. Nonequivalence of chlorine atoms which are bound to the metal atom, relate to nonequivalence of halogen atoms in the complexesM ₂(μ?S₂)₂ X ₈ ^2? . Chlorine atomstrans to SeCl₂ ligands form short bonds with the metal; the corresponding³⁵Cl NQR frequency is increased. The selenium dichloride ligand is ambidentate. The selenium atom binds as a donor to the metal and as an acceptor to two chlorine atoms which are also bound covalently to the same metal atom.     

Syntheses and Crystal Structures of Two New Iron-sulfur Carbonyl Complexes: [Fe_2(SC_6H_4Cl)_2(CO)_6]·0.5(Et_2O) and [Fe_3(SC_6H_4NH_2)_6(CO)_6]·2(MeOH)

Two new iron-sulfur carbonyl complexes, [Fe2(SC6H4Cl)2(CO)6]?0.5(Et2O) 1 and [Fe3(SC6H4NH2)6(CO)6]?2(MeOH) 2, have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Crystal data for 1: monoclinic, C2/c, a = 18.4439(8), b = 11.0999(5), c = 25.1830(10) ?, β = 97.0370(10)o, V = 5116.8(4) ?3, Z = 8, C20H13Cl2Fe2O6.50S2, Mr = 604.02, Dc = 1.568 g/cm3, μ = 1.540 mm–1, F(000) = 2424, the final R = 0.0545 and wR = 0.1454 for 3443 observed reflections with I > 2σ(I); 2: monoclinic, P21/n, a = 12.350, b = 26.3050(11), c = 16.057 ?, β = 97.891(3)°, V = 5166.9(2) ?3, Z = 4, C44H44Fe3N6O8S6, Mr = 1144.76, Dc = 1.472 g/cm3, μ = 1.128 mm–1, F(000) = 2352, the final R = 0.0442 and wR = 0.1197 for 7978 observed reflections with I > 2σ(I). Complex 1 contains one iron dimer, in which two tricarbonyliron(I) fragments are bridged together by two 4-chlorophenylthiolate ligands, whereas complex 2 contains a linear tri-iron cluster, in which two terminal tricarbonyliron(II) fragments and the central Fe(II) atom are linked together by six 4-aminophenylthiolate bridging ligands.     

[Eu2(o-ClC6H4OCH2COO)6(C12H8N2)2(H2O)2]·(CH3)2SO的晶体结构和荧光光谱

标题配合物Ｍ＝１８９２．０１,单斜晶系,空间群Ｐ２１／ｃ,ａ＝１．２９７５（３）ｎｍ,ｂ＝２．６５９１（９）ｎｍ,ｃ＝１．２１１８（３）ｎｍ,β＝９６．９５（１）°,Ｚ＝２,Ｄｃ＝１．５７７ｇ／ｃｍ３,Ｔ＝２９３（２）Ｋ。最终的偏离因子Ｒ＝０．０５８３。该配合物以二聚体形式存在,通过其中的桥联羧基形成了双核分子。该分子中羧基具有桥联双齿、桥联三齿和单齿三种配位模式,Ｅｕ－Ｅｕ之间的距离为０．４０１９（１）ｎｍ。在７７Ｋ下测得配合物中Ｅｕ（Ⅲ）离子仅有一种格位。５Ｄ０→７ＦＪ（Ｊ＝０～２）跃迁光谱说明Ｅｕ（Ⅲ）离子格位具有Ｃ２对称性。     

配合物Ru(dcbpy)(phen)2(PF6)2的2D-NMR分析

用一维ＮＭＲ方法研究了新型电化学发光探针Ｒｕ（ｄｃｂｐｙ）（ｐｈｅｎ）２（ＰＦ６）２的立体结构,借助二维＾１Ｈ－＾１Ｈ ＣＯＳＹ和＾１Ｈ－＾１３Ｃ ＣＯＳＹ实验对其氢谱和碳谱进行了完全的归属,并给出了其氢谱和碳谱的化学位移值。     

Structure of bis(hexamethylenetetramine) hexaaquanickel(II)hexafluorotitanate(IV) monohydrate — [Ni(OH2)6][TiF6](Ur)2·H2O

The X-ray diffraction study of a single crystal with the composition NiTiF₆(Ur)₂·7H₂O is performed, where Ur = C₆H₁₂N₄ is an urotropine (hexamethylenetetramine) molecule. The compound crystallizes in the triclinic P-1 space group: a = 8.7220(5) Å, b = 9.1004(5) Å, c = 17.533(1) Å, α = 75.074(1)°, β = 88.530(1)°, γ = 62.558(1)°, Z = 2, d _x = 1.756 g/cm³, μ = 1.228 mm^?1, R = 0.0351. The crystalline compound is ionic. The structural unit consists of [Ni(OH₂)₆]²⁺ and [TiF₆]^2? ions and Ur and H₂O molecules. The structural formula of the compound is [Ni(OH₂)₆][TiF₆](Ur)₂·H₂O. Hydrogen bonds in the compound are studied and analyzed.     

Eu2(3,4-DMBA)6(PHEN)2的晶体结构及HRS研究

合成了铕（Ⅲ）与３,４－二甲基苯甲酸（３,４－ＨＤＭＢＡ）、邻菲咯啉（ＰＨＥＮ）形成的晶体配合物Ｅｕ２（３,４－ＤＭＢＡ）６（ＰＨＥＮ）２．测定其分子量Ｍ＝１５５９．３５,晶体属三斜晶系,Ｐ１空间群,ａ＝１．２６６５（４）ｎｍ,ｂ＝１．３５６７（４）ｎｍ,ｃ＝１．０７５５（４）ｎｍ,α＝９８．８７（３）°,β＝１０８．２５（３）°,γ＝８７．９８（２）°,Ｚ＝１,最终的偏离因子Ｒ＝０．０３１．以Ｅｕ（Ⅲ）离子为荧光探针,在７７Ｋ下测定了配合物的高分辨光谱（ＨＲＳ）．铕配合物的激发光谱、发光光谱、时间分辨光谱和发光寿命测定结果表明,该配合物中存在两种化学环境不同的Ｅｕ（Ⅲ）离子格位     

[(C_6H_5NO_2)Pr(H_2O)_4](CrMo_6O_(24)H_6)·(C_6H_5NO_2)·2.5H_2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[(C6H5NO2)2Pr(H2O)4](CrMo6O24H6)·2.5H2O,通过红外光谱和X射线单晶衍射对其进行了表征.结果表明,该化合物属于单斜晶系,C2/c空间群.a=2.3442(9)nm,b=1.3291(5)nm,c=2.458(1)nm,β=103.08(1)°,V=7.460(5)nm3,R1=0.0727,wR2=0.1903.结构分析表明,[CrMo6O24H6]3-阴离子通过端氧担载一个配位的Pr3+离子形成中性的(C6H5NO2)Pr(H2O)4(CrMo6O24H6)基团,相邻的中性基团在Ot—Pr—Ot桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构.     

La_6NiSi_2S_(14)与La_6CoSi_2S_(14)的合成及其晶体结构

La_6NiSi_2S_(14)与La_6CoSi_2S_(14)单晶是利用助熔剂法在1100℃下合成的。它们皆属于六方晶系,P6_3空间群。a=10.293(1)[10.290(2)] A,c=5.744(1)[5.763(2)]A,Z=1。627[629]条反射(I≥2.5σ(I))参加计算,R=0.0363[0.0781]。La在扭曲的二帽三角棱柱内,与S八配位,La-S平均键长为2.990[2.992]A。Ni[Co](处于B位)在三角反棱柱里,与S六配位,Ni[Co]-S健长三个是2.559[2.529]A,其余三个为2.650[2.679]A,其占有率约为1/6。Si(处于C位)在四面体内,与S四配位,在Si-S键长中三个是2.130[2.146]A.第四个键长是2.098[2.093]A。     

X-ray Crystal Structure of (CNSSS)2(M)2 (M = AsF6 −, SbF6 −, Sb2F11 −)

The crystal structures of (CNSSS)₂(AsF₆)₂, (CNSSS)₂(SbF6)₂, and two phases of (CNSSS)₂(Sb₂F₁₁)₂ have been determined. The AsF₆ ^?, SbF₆ ^?, and α-Sb₂F₁₁ ^? salts crystallize as reddish-brown plates whereas the β-Sb₂F₁₁ ^? salt crystallizes as green rods. The dication ^ß+SSSNCCNSSS^+ß (1²⁺) is the same in all four structures and consists of two 7π rings linked by a sp²-sp² C-C bond (1.462 Å in 1 (AsF₆)₂). The packing in the four structures is similar with stacks of dications along the a-axis and alternating sheets of dications and anions lying in the bc-plane. The differences in the dication-dication contacts is reflected in the variable temperature magnetic data.     

Tetranuclear bismuth complexes Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H6 and Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H4Me2-1,4: Synthesis and structures

X-ray diffraction study of tetranuclear organobismuth complexes Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2⁶-C₆H₆ and Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2(C₆H₄Me₂-1,4) revealed four Bi atoms connected through the bridging carboxylate ligands and the O atoms. The coordination sphere of the terminal Bi atoms includes the chelate carboxylate ligand and the 6-arene molecule. The bridging O atoms are tricoordinated, the distances between the terminal Bi atom and the center of benzene molecule (1,4-dimethylbenzene) are 3.024 Å(3.131 Å).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 4–11.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Sharutina, Ivanenko, Adonin, Starichenko, Pushilin, Gerasimenko.     

(enH_2)_5[(VO)_(12)O_6B_(18)O_(36)(OH)_6]·2(H_3O)·6H_2O的水热合成和晶体结构

以NH4VO3,H3BO3,乙二胺,MoO3,H2O为原料,按物质的量比2∶20∶9∶3∶222,在180℃条件下晶化,得到黑色棱形晶体(enH2)5[(VO)12O6B18O36(OH)6].2(H3O).6H2O.单晶结构分析结果表明该化合物属三斜晶系,Pī空间群,晶胞参数a=1.336 8(3)nm,b=1.599 8(3)nm,c=1.663 4(3)nm,α=94.040(1)°,β=91.530(1)°,γ=95.830(1)°,V=3.528 1(12)nm3,Z=2,Dc=2.099 g/cm3,μ=1.649 mm-1,F(000)=2 228,15 641个可观察独立衍射点射点(I>2σ(I)),最后结构精修到偏离因子R1=0.047 5,wR2=0.150 4,S=1.039.该化合物的结构主要由阴离子簇[(VO)12O6B18O36(OH)6]12-构成.该阴离子簇由B18O36(OH)6十八元环夹在两个以共边交替相连形成的V6O18簇中间,通过共用氧原子形成三明治式结构新颖的硼-钒-氧离子簇,簇间填充了一些(enH2)2+离子和水分子.     

Syntheses and characterization of the vanadium trimer (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(4,4′-bipyridine) and the vanadium hexamer [(V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6]2(μ2-N1,N2-di(pyridin-4-yl)oxalamide)

Reacting VO(acac)₂ with six equivalents of dibenzylphosphinic acid in the presence of 4,4′-bipyridine or μ₂-N¹,N²-di(pyridin-4-yl)oxalamide leads to trimeric (V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆(4,4′-bipyridine) or the hexamer [(V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆]₂(μ₂-N¹,N²-di(pyridin-4-yl)oxalamide). The complexes were characterized by spectroscopic (FTIR and ¹H NMR spectroscopies), TGA, and by single crystal X-ray diffraction measurements. The structures consist of a planar central core where three vanadium ions are arranged in the form of a quasi-isosceles triangle and contain an interstitial O which is multiply bonded to one V and weakly interacting at different bond distances to the remaining two V ions.