簇合物[(η5-C5Me5)WS3{Cu(PPh3)}3Cl](PF6)的合成及晶体结构

Reaction of a preformed cluster [{(η⁵-C₅Me₅)WS₃}₃Cu₇(MeCN)₉](PF₆)₄ (1) in MeCN with LiCl and PPh₃ gave rise to a tetranuclear cationic cluster [(η⁵-C₅Me₅)WS₃{Cu(PPh₃)}₃Cl](PF₆) (2). The title compound 2 was characterized by elementary analysis, IR, UV-Vis, ¹H NMR, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2₁/c with a=1.799 8(4) nm, b=2.083 6(4) nm, c=1.913 5(4) nm, β=113.63(3)°, V=6.574(3) nm³, Z=4. The cluster cation [(η⁵-C₅Me₅)WS₃{Cu(PPh₃)}₃Cl]⁺ of 2 contains a strongly distorted, cubane-like structure [WS₃Cu₃Cl] in which one Cl weakly fills into the void of the nido-like [WS₃Cu₃] fragment with three relatively long Cu-Cl distances. CCDC: 270415.     

簇合物Co3(CO)7(μ3-S)[μ,η2-CNP(S)(C6H4OCH3)OC(Ph)CH]和Co3(CO)7(μ3-S)[μ,η2-SCNC(CH3)2P(S)(Cl)N(Ph)]的合成与晶体结构

用Co₂(CO)₈分别与两个杂环配体C(S)NHP(S)(C₆H₄OCH₃)OC(Ph)CH (L₁)和C(S)NHC(CH₃)₂P(S)(Cl)N(Ph) (L₂)反应,合成两个新的三核钴羰基硫簇合物Co₃(CO)₇(μ₃-S)[μ,η²-CNP(S)(C₆H₄OCH₃)OC(Ph)CH](Ⅰ)和Co₃(CO)₇(μ₃-S)[μ,η²-SCNC(CH₃)₂P(S)(Cl)N(Ph)](Ⅱ)。用元素分析,IR, ¹H NMR, ³¹P NMR及MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,空间群P1,Ⅰ的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.601(3)°,γ=88.535(2)°,V=1.4318(5)nm³,Z=2,D_c=1.641g·cm^-3,F(000)=716,μ=1.893mm^-1,R=0.0602,R_w=0.1515。Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm³,Z=2,D_c=1.841g·cm^-3,F(000)=690,μ=2.419mm^-1,R=0.0423,R_w=0.1075。Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有CO作为端基配体与三个Co原子成键。Ⅰ中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件。     

半开口立方烷型簇合物[WOS3Cu3I(4-bpy)3]·0.25EtOH的合成及晶体结构(4-bpy=4-叔丁基吡啶)

Reaction of (NH₄)₂[WOS₃] with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster [WOS₃Cu₃I(4-bpy)₃]·0.25EtOH. This compound was characterized by elementary analysis, IR, ¹H NMR, TGA, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2/c with a=2.220 9(2) nm, b=1.364 66(11) nm, c=2.490 6(2) nm, β=104.953(2)°, V=7.292 9(12) nm³, Z=4. The title compound may be viewed as having a half-open cubane-like structure in which three [Cu(4-bpy)]⁺ units are linked by a triply-bridging [WOS₃]^2- unit and a doubly-bridging iodine atom. CCDC: 266412.     

茂金属配合物[Mo(eta5-C5H4Si2Me5)(CO)3Cl]的晶体结构和量子化学研究

The crystal structure of tricarbonylpentamethyldisilanylcyclopentadienyl chloro-molybdenum complex [Mo(eta⁵-C₅H₄Si₂Me₅)(CO)₃Cl] has been determined by X-ray diffraction method.A quantum chemistry calculation by means of G98W package and taking LanL2DZ basis set.The crystal belongs to orthorhombic space group Pbca with a=1.5812(5), b=1.7307(3), c=1.3339(2)nm,V=3.650(1)nm³, Z=8, D_c=1.495 g·cm^-3, μ(MoKα)= 9.97cm^-1,F(000)=1664,final R=0.027 for 2590 unique reflection [I >3σ(I)]. The bond lengths of Mo-Cl and is 0.250nm,and Mo-CO is 0.198～0.202nm. The Mo atom has a distorted tetrahedral cone geometry.     

[Cu(Ⅱ)(DETA)]3[Cr(CN)6]2·5H2O(DETA=二乙烯三胺)氰桥配合物的结构和磁性研究

A new coordination complex [Cu(Ⅱ)(DETA)]₃[Cr(CN)₆]₂·5H₂O (DETA=diethylenetriamine) was synthesized, its crystal structure and magnetic properties were determined. The crystal crystallizes in monoclinic space group P2₁/c, with unit cell constants a=2.056 6(7) nm, b=1.440 7(5) nm, c=1.513 3(5) nm, β=95.996(6)°, and V=4.459(3) nm³, Z=4, D_c=1.499 g·cm^-3, F(000)=2 060，μ(Mo Kα)=1.936 mm^-1, R₁=0.052 3, wR₂=0.106 2. The structure consists of a one-dimensional chain of [Cu(DETA)]₂[Cr(CN)₆]⁺ and binuclear [Cu(DETA)][Cr(CN)₆]^-. The coordination geometries around Cu²⁺ atoms are distorted square-based pyramidal and distorted square, respectively. Magnetism studies show that there are ferromagnetic interactions between Cu²⁺ and Cr³⁺ ions. CCDC: 272213.     

二个新颖的一维聚合物{(PyH)3[Cu3Br6]}∞和{(γ-MePyH)2[Cu2Br4]}∞的合成和晶体结构

Reactions of CuBr with equimolar PyHBr or γ-MePyHBr afforded two novel one-dimensional bromocuprate(Ⅰ)polymers {(PyH)₃[Cu₃Br₆]}_∞ (1) and {(γ-MePyH)₂[Cu₂Br₄]}_∞(2)， respectively. Both 1 and 2 were charac-terized by IR， elemental analysis， and X-ray crystallography. Crystal data for 1: monoclinic， space group P2₁/n， a=0.93262(12)nm， b=1.3497(2)nm， c=1.9149(2)nm， β=93.465(7)°， V=2.4060(5)nm³， Z=4. Crystal data for 2: orthorhombic， space group Pbcm， a=0.8659(4)nm， b=1.5669(6)nm， c=1.2849(5)nm， V=1.7432(2)nm³， Z=4. The structure of 1 has a unique helical chain composed of [Cu₃Br₅] units and μ-bromide anions while that of 2 shows a linear chain consisted of [Cu₂(μ-Br)₂] units bridged by pairs of μ-Br atoms. CCDC: 1， 208412; 2， 208413.     

簇合物[WS4Ag3(PPh3)3{S2P(OCH2Ph)3}]的合成、晶体结构及非线性光学性质

本文用(NH₄)₂WS₄，Ag[S₂P(OCH₂Ph)₂]和PPh₃为原料合成了簇合物[WS₄Ag₃(PPh₃)₃{S₂P(OCH₂Ph)₃}]，并得到了晶体。晶体属正交晶系，空间群为P2₁2₁2₁，晶胞参数a=1.32370(4)nm，b=1.34427(4)nm，c=3.83246(11)nm。X-射线单晶结构测定结果表明它具有巢状分子结构，配体(PhCH₂O)₂PS₂^-(简称dtp)的两个S原子中的一个硫原子仅与一个金属原子配位，另一个硫原子则同时与两个金属原子配位。簇合物的非线性光学性质用脉宽8ns激光在532nm波长进行了研究。该化合物表现为一定的光学吸收和强的自聚焦效应，其三阶非线性吸收系数α₂=1.50×10^-10m·W^-1，折射系数n₂=2.45×10^-11esu。     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

Cu[C5H3N(CCH3=N-C6H5)2]2(PF6)2配合物的合成、晶体结构和热分解反应动力学

The title complex Cu[C₅H₃N(CCH₃=N-C₆H₅)₂]₂(PF₆)₂ has been synthesized by reaction of Schiff base C₅H₃N(CCH₃=N-C₆H₅)₂ and cupric sulfate in toluene solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 1041.85. The crystal structure belongs to triclinic system with space group P1 and cell parameters: a=12.6470(10)?, b=14.123(2)?, c=15.613(2)?;α=66.150(10)°,β=79.470(10)°,γ=78.290(10)°, V=2481.6(5)?³, Z=2, D_c=1.394Mg·m^-3 and F(000)=1064. The final R[I >2σ(I)]:R₁=0.0668, wR₂=0.1927; R(all data): R₁=0.1133, wR₂=0.2357. The Cu(Ⅱ) was coordinated by six nitrogen, at the same time the Cu(Ⅱ) formed a distorted octahedron, besides the angles and planes of this compound were discussed . The result of kinetics of the thermal decomposition indicated that the first step of it is 2 series chemical reactions, the function of machanism is f(a)=(1-a)², and the activation energy is 144.64E/kJ. CCDC: 180872.     

Synthesis and Structural Characterization of [Cu(DMF)_6][(η~5-C_5Me_5)WS_3(CuBr)_3]_2·Et_2O

1 INTRODUCTION In the last decade, we have been interested in the synthesis of [PPh4][(h5-C5Me5)MS3] (M = Mo, W)[1, 2] , Whose organometallic trisulfido anions show high reactivity towards various transition metals[3~6] . We once reported that the reaction of [PPh4][(h5-C5Me5)WS3] with CuBr in CH3CN afforded a double incomplete-cubane cluster [PPh4]2[(h5-C5Me5)WS3(CuBr)3]2[3], while the analogous reaction of [PPh4][(h5-C5Me5)WS3] with CuBr in CHCl3 gave rise to a 揻our-…     

[(η5-C5Me5)WS3Cu3Br2(PPyPh2)2]四核簇合物的合成和晶体结构

以2[(η5-C5Me5)WS3(CuBr)3]2和diphenyl-2-pyridylphosphine (PPyPh2)在乙腈中反应得到标题化合物[(η5-C5Me5)WS3Cu3Br2(PPyPh2)2], 对该产物进行了元素分析、 IR、 UV-Vis和1H NMR 谱表征, 并测定了晶体结构. 该化合物晶体属三斜晶系, P1空间群, 晶胞参数: a=1.545 9(7) nm, b=1.62 0(1) nm, c=1.018 0(2) nm, α=94.18(3)°, β=97.38(3)°, γ=111.81(4)°, V=2.327(2) nm3, Z=2, Dc=1.84 g*cm-3, F(000)=1 260, μ=57.77 cm-1, 最终偏离因子R=0.029. 此簇合物结构可视为由一个[(η5-C5Me5)WS3]单元和3个Cu组成的开口立方烷, 其中2个Cu是畸变四面体配位, 第3个Cu是近似三角平面配位. W-Cu(1), W-Cu(2) 和W-Cu(3)距离分别为0.270 41(9), 0.273 27(8), 0.267 85(9) nm.     

Syntheses and Characterizations of （η~5－C_5H_5）MoFeCo（CO）_8（μ_3－S） and （η~5－C_5H_5）_2Mo_2Fe（CO）_7（μ_3－S）：X－ray Crystal Structure of （η~5－C_5H_5）MoFeCo（CO）_8（μ_3－S）

ＳｙｎｔｈｅｓｅｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｓｏｆ（η~５－Ｃ_５Ｈ_５）ＭｏＦｅＣｏ（ＣＯ）_８（μ_３－Ｓ）ａｎｄ（η~５－Ｃ_５Ｈ_５）_２Ｍｏ_２Ｆｅ（ＣＯ）_７（μ_３－Ｓ）：Ｘ－ｒａｙＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ（η~５－Ｃ_５Ｈ_...     

Mo－Cu－S原子簇化合物［Mo_2Cu_6S_6（SCMe_3）_2（O）_

基于标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。     

Structural Characterization of Chiral Sulfido Cluster(η~5-C_5H_5) WFeCo(CO)_8 (μ_3-S)

1INtrODUCTIONThethiophilicpropertyoftransitionmetalshasbeensuccessfullyusedforthesynthesisofsulfidocluster[li.ComPOundscontainingsulfidoligandsareimportantinvariousareasofmodernchemistry"--".WehaverePOrtedthesynthesesandstructuresofaserialmixedsulfidoclustersts'6i.Theelectrophilic--additionsubstituenteliminationreactionmechanismwasalsoproPOsed.Asapartofcontinuouswork,herewereportthesynthesisandcharacterizationofthetitlecluster.2EXPERIMENTALAlloperationswerecarriedoutunderhighlypure…     

Synthesis, Structure and Optical Limiting （OL） Properties of a Novel Incomplete Cubane-like Cluster [PPh4][η^5-C5Me5） WS3-（CuBr） （CuI）2 （μ-dppm）]

IntroductionTetrathiometallateanions [MS4 ]2 - (M =Mo ,W )andtheirclusterswithvarioustransitionmetalsarewell knownfortheirrichcoordinationchemistry ,1 7andtheirrelationtoindustrialcatalysisprocess ,8biologicalsystems ,9andNLOmaterials .10 12 However,thechemistryoftheorganometallictrisulfidecomplexes [PPh4 ][(η5 C5Me5) MS3](M =Mo ,13W14 )andtheirrelatedmixed metalclus tershavebeenlessinvestigated .15,16 Inordertoextendourknowledgeaboutthechemistryof [PPh4 ][(η5 C5Me5) MS3]andconti…     

Heterometallische Clusterkomplexe der Typen Re2(μ-PR2)(CO)8(HgY) und ReMo(μ-PR2)(η5-C5H5)(CO)6(HgY) (R = Ph,Cy; Y = Cl,W(η5-C5H5)(CO)3)

Heterometallic Cluster Complexes of the Types Re₂(μ-PR₂)(CO)₈(HgY) and ReMo(μ-PR₂)(η⁵-C₅H₅)(CO)₆(HgY) (R = Ph, Cy; Y = Cl, W(η⁵-C₅H₅)(CO)₃) Dinuclear complexes Re₂(μ-H)(μ-PR₂)(CO)₈ and ReMo(μ-H)(μ-PR₂)(η⁵-C₅H₅)(CO)₆ (R = phenyl, cyclohexyl) were deprotonated and reacted as anions with HgCl₂ to compounds of the both types Re₂(μ-PR₂)(CO)₈HgCl) and ReMo(μ-PR₂)(η⁵-C₅H₅)(CO)₆(HgCl). The heterometallic three-membered cluster complexes correspond to an isolobal exchange of a proton against a cationic HgCl⁺ group. For one of the products ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgCl) has been shown its conversion with NaW(η⁵-C₅H₅)(CO)₃ to ReMo(μ-PCy₂)(η⁵-C₅H₅)(HgW(η⁵-C₅H₅)(CO)₃) under substitution of the chloro ligand, par example. The newly prepared compounds were characterized by means of IR, UV/VIS and ³¹P NMR data. A complete determination of the molecular structure by single crystal analyses was done in the case of Re₂(μ-PCy₂)(CO)₈(HgCl) and of ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgCl) which both are dimer because of the presence of an asymmetric dichloro bridge, and of ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgW(η⁵-C₅H₅)(CO)₃). The structural study illustrates through comparison the influence of various metal types on an interaction between centric and edge-bridged frontier orbitals in three-membered metal rings.     

Synthesis and Characterization of the Chiral Skeleton Cluster [NiRuMo(CO)_5(μ_3-S)(η~5-C_5H_5)(η~5-C_5H_4COCH_3)]

1 INTRODUCTION The chemistry of transition metal cluster has enjoyed an exceptional growth since the mid 1970s[1, 2], especially in recent years the structural and bonding aspects of mixed-metal tetrahedral skeleton clusters have been extensively studied[3]. One important reason is that such chiral cluster can induce an asymmetric catalysis potentially. In our research group, considerable efforts have been directed to the synthesis of chiral tetrahedral clusters containing four different…