[(O)MoCu_3(μ_3-S)_3(μ_3-Cl)(PPh_3)_3]·2THF的合成及其晶体结构

固体化合物(NH_4)_6Mo_7O_(24)·4H_2O和(PPh_3)_2CuCl与饱和液体NH_4HS反应获得桔红针状标题晶体。晶体空间群为P2_1/c,晶胞参数a=11.742(2),b=28.186(7),c=19.304(3),β=100.57(2)°,V=6280.4(?)~3,D_c=1.46g/cm~3,Z=4,F(000)=2816。在3≤2θ≤45°范围内收集到8414个独立衍射强度数据,其中3856个I≥1.5σ(I)强度数据参加结构计算。标题化合物分子是以{MoCu_3S_3Cl}类立方烷型簇为核心的分子,Mo—Cu的平均距离为2.716。     

Studies on solid state reactions of coordination compounds LI.Solid state syntheses of a family of Ag-Mo(W)-S cubane-like cluster compounds:Crystal structures of{Ag_3MoS_3I}(PPh_3)_3S and{Ag_3WS_3Cl}(PPh_3)_3S·0.5P(S)Ph_3·3H_2O~+

Reactions of[NH_4]_2[MS_4](M=Mo,W),AgX(X=Cl,Br,I,CN,SCN)and PPh_3in the solid state produced six new mixed-metal sulfur containing cluster compounds,two ofwhich,{Ag_3MoS_3I}(PPh_3)_3S(1)and{Ag_3WS_3Cl}(PPh_3)_3S·0.5P(S)Ph_3·3H_2O(2),were determinedby single crystal X-ray analysis.The crystal data:1,triclinic,P,a=12.114(2),b=13.420(2),c=20.346(3),α=74.53(1),β=86.73(1),γ=63.74(1)°,Z=2,R=0.043 for 4805 independentdata;2,hexagonal,R3,a=b=16.201(3),c=45.091(10),Z=6,R=0.042 for 2729 independentdata.The central unit{Ag_3MS_3X}(M=Mo,W;X=Cl,I)of the two compounds can be des-cribed as a slightly distorted cube,four corners being formed by the MS_4~(2-) ligand(with a ter-minal S atom).The remaining corners are occupied by one X(Cl or I)atom and three Agatoms(with one PPh_3 ligand bound to each of the latter).The generation of different types ofAg-Mo(W)-S cluster compounds prepared from solid state reactions under different reactiontemperatues is discussed.     

固相配位化学反应研究(LXI)——[Cu(SC(Ph)NHPh)(PPh_3)_2X](X+Cl,Br,I)的固相合成和晶体结构(X=Cl)

SC(Ph)NHPh,CuX(X=Cl,Br,I)和PPh_3的固相反应产物经CS_2处理得红黄色立方晶体[Cu(SC(Ph)NHPh)(PPh_3)_2X],其中X=Cl的单晶用X射线衍射法收集晶胞参数,此晶体属单斜晶系,空间群P2_1/c,α=1.8013(5)nm,b=1.4588(5)nm,c=1.7222(4)nm,β=105.54(3)°,F=4.3601nm~3,Z=4。中心铜离子以扭曲四面体配位,Cu原子周围的平均键角为109.4°,其中Cu—S键、Cu—Cl键、Cu—P(1)键和Cu—P(2)键的键长分别为0.2352(3)nm、0.2375(4)nm、0.2297(4)nm和0.2282(3)nm.     

A bi-butterfly W-Cu-S cluster compound:Synthesis and crystal structure of(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]

The compound(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]was obtained by the reaction of Bu_4NBr,(NH_4)_2WS_4,NaS_2NCC_4H_8 and CuCl in CH_3CN and CH_3OH.It crystallizes in the monoclinicspace group P2_1/c with unit cell parameters:a=21.875(5),b=16.843(4),c=17.745(5),β=101.69(6)°,V=6402(6)~3,Z=4,D_o=1.718 g·cm~(-3).The final R and R_w values converged to 0.055and 0.060 respectively.The structure consists of two‘butterfly’units[WS_4Cu_2]linked togetherby two weak Cu—S bonds and two bridging S_2CNC_4H_8 ligands.Infrared spectra gave charac-teristic absorptions at 495 cm~(-1) for W=S and 450,435,412 cm~(-1) for W—μ-S.     

固相配位化学反应研究(ⅩⅩⅩⅩⅣ)——[C_5H_5N(C_(16)H_(33))]_4[Cu_4Br_8]的固相合成和晶体结构

(NH_4)_2MoS_4、CuBr和(C_(16)H_(33))C_5H_5NBr·H_2O固相反应产物,经CH_2Cl_2/CH_3OH处理得黄色菱形晶体[C_5H_5N(C_(16)H_(33)]_4[Cu_4Br_8],晶体属三斜晶系,空间群为P1,a=0.9762(2)nm,b=3.1948(4)nm,c=0.9143(2)nm,α=94.71(1)°,β=116.48(2)°,γ=92.54(1)°Z=1.晶体中含以Br~-为桥基连接的四核铜(Ⅰ)链状阴离子,四配位铜原子的Cu—Br平均距离为0.2664nm,三配位的钢原子的Cu—Br的平均距离为0.2517nm,铜原子间的距离为0.296～0.320nm.     

铂氢化物trans-[PtH(tu)(PPh_3)_2]Cl(tu)(THF)_2(tu=SC(NH_2)_2)的结构

制得含硫脲配体的铂氢化物单晶trans-[PtH(tu)(PPh_3)_2]Cl(tu)(THF)_2,其结构测定结果为:C_(46)H_(55)N_4O_2P_2S_2ClPt M=1052.6,单斜晶系,空间群为 P2_1/c,a=12.103(1),b=21.619(3),c=20.189(4)(?),β=103.31(0)°,V=5140(2)(?)~3,Z=4,D_c=1.360g·cm~(-3),F(000)=2128,R=0.050,R_w=0.063.Pt(Ⅱ)与两个磷、一个硫脲分子的硫和一个氢相配合,形成四边形配位。     

直接法合成异核羰基金属簇合物及Pd_3(SC_6H_4OH)_3(PPh_3)_3(OH)_2Cl的晶体结构分析

本文根据分子碎片结合原理,用直接法由简单的单质元素,金属盐类及配体,通过控制反应温度,压力,时间及配体用量在CO气氛下一步合成含羰基和不含羰基的簇合物:Pd_3(SC_6H_4OH)_3(PPh_3)_3(OH)_2Cl(1),Fe_2S_2(CO)_5Pd(PPh_3)_3(2),Fe_2S_2(CO)-5Pt(PPh_3)_3(3).对它们进行了IR,NMR,EDS,元素分析,金属分析和化合物1的X光单晶衍射结构分析.化合物1属单斜晶系,离子型,P2_1/n空间群,晶胞参数a=1.4629(3)nm,b=1.9263(3)nm,c=2.4908(7)nm,β=94.53(2)°,Z=4,R=0.053.     

STUDIES ON SOLID STATE REACTIONS OF COORDINATION COMPOUNDS(LXⅡ)Solid state synthesis and crystal structure of the complex ICu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)CIJ·0.5CS_2

[Cu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)Cl]·0.5CS_2=,Mr=895.79,monoclinic,spacegroup P2_1/a,a=17.231(3),b=14.611(2),c=18.000(3) ,β=105.56(2)°,V=4365(1) ~3,Z=4,D_c=1.37g/cm~3.,λ(MoK_α)=0.71073 ,μ=12.15cm~(-1),F(000)=1855,R=0.052,R_W=0.045 for 3930 observed reflections with Ⅰ>1.5σ(Ⅰ).The central metal atom has a dis.torted tetrahedral geometry with bond lengths Cu-S=2.384(2) (Au-S=2.389(4)),Cu-Cl=2.481(3)(Au-Cl=2.474(1))and Cu-P=2.269(2)-2.289(2)(Au-P=2.270(4)-2.279(4)) .     

[WS4Cu2（Py）4]的合成及晶体结构

(NH_4)_2WS_4、CuCl和(n-Bu)_4NBr在Ar气氛中,90℃下反应10 h,所得产物先后经CH_2Cl_2与CH_3OH处理,得一桔红色晶体。该晶体与吡啶反应,即得到桔红色针状晶体[WS_4Cu_2(Py)_4],属单斜晶系,空间群C2/c,晶胞参数:a=14.109(1),b=12.704(1),c=14.071(1);β=96.97(1)°;Z=4。结构用重原子法解出,经最小二乘法修正,偏离因子R=0.027。     

杂氮三环化合物晶体的X射线衍射研究——Ⅱ.1-氯丙基-2,8,9-三氧杂-5-氮杂-1-硅三环[3,3,3,0~(1.5)]十一碳烷-3-酮的晶体与分子结构

题目所指的化合物(NC_6H_(10)O_4Si-CH_2CH_2CH_2Cl)属正交晶系,所属空间群为P2_12_12_1。晶胞参数:a=12.943,b=11.477,c=8.273。Z=4。取1243个可观测独立反射数据,用直接法和Fourier综合解得粗结构,经最小二乘修正,偏离因子R为0.049。三个五员环(Si,O,C,C,N)都有一个较大的扭角,分别为23.7°,41.6°,42.8°。其中带羰基环的最大扭角相对较小(23.7°)。三环最小二乘平面间夹角接近120°,分子中的氯丙基-CH_2CH_2CH_2C1近乎在一个平面上折叠。     

SYTHESE AND REACTIONS OF HETEROBINUCLEAR COMPLEXES [PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2] (M = Mo, W)

Abstract The complexes [M(CO)_3(CH_3CN)_3](M=Mo, W)react with an equimolar quantity ofPhSnCl_3 in dichloromethane at room tempreture to afford new heterobinuclearcomplexes [PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2] [M=Mo(1); W(2)]. The complexes reactwith two equivalents of PR_2R'(R=Ph, R'=Ph, Me; R=Cy, R'=H) to yield stablecomplexes [PhCl_2SnM(Cl)(CO)_3(PR_2R')_2]. Reaction of[PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2]with one equivalent of PPh_2(CH_2)nPPh_2(n=I,2) or bulky phosphine ligands PBu_2~tClin dichloromethane at room tempreture to give [PhCl_2SnMo(Cl)(CO)_3{PPh_2(CH_2)n-PPh_2}] .CH_2Cl_2, [PhCl_2SnMo(Cl)(CO)_3PBu_2~tCl]. CH_2Cl_2, respectively. The complexes1 and 2 react with phosphite donor ligands P(OMe)_3 to give [PhCl_2SnM(Cl)(CO)_2-{P(OMe)_3}_3]. All complexes have been characterized by elemental analysis, IRand ~1HNMR spectroscopies. Here we report the preliminary results of this work.     

[Tb(CH_3COO)_3(H_2O)_2]_2的合成及其结构测定

2-羟基吡啶、希土高氯酸盐和乙酸钴在乙腈中反应,制备了九配位化合物[Tb(CH_3COO)_3·2H_2O]_2该晶体为三斜晶系,P~(?)空间群,其晶胞参数为a=8.870(4)(?),b=9.247(1)(?),c=10.586(1)(?),α=65.13(1)°,β=64.43(2)°,γ=62.16(4)°,V=665.97(?)~3,Z=1,F(000)=394。测定了配合物的红外光谱。讨论了它的生成机制。     

Fe3(CO)12与P(NEt2)2Cl的反应--两核和三核铁羰基簇合衍生物的合成和晶体结构

Fe_3(CO)_(12)与配位基前体P(NEt_2)_2Cl反应,给出4个新的两核和三核铁羰基簇合衍生物:Fe_2(CO)_6(μ-Cl)[μ-P(NEt_2)_2](Ⅰ),Fe_2(CO)_6[μ-P(NEt_2)_2]_2(Ⅱ),Fe_3(CO)_9(μ-CO)(μ_3-PNEt_2)(Ⅲ)和Fe_3(CO)_9(μ_3-PNEt_2)[P(NEt_2)_3](Ⅳ)。在反应期间,配前体分子中的P-Cl和P-N键劈开,形成的分子片Cl、PNEt_2、P(NEt_2)_2和P(NEt_2)_3作为配体与铁羰合物重新组建成上述簇合物。利用X射线衍射法测定了它们的晶体结构。Ⅰ属三斜晶系,P1空间群,晶胞参数a=0.8745(6)nm,b=0.9601(7)nm,c=1.3996(10)nm,α=74.131(11)°,β=79.480(12)°,γ=69.727(12)°,V=1.0553(13)nm~3,D_c=1.543g·cm~(-3),Z=2,R=0.0443,wR=0.0831。Ⅱ属正交晶系,Pbcn空间群,晶胞参数a=1.0153(3)nm,b=1.7543(5)nm,c=1.6860(5)nm,V=3.0031(15)nm~3,D_c=1.394g·cm~(-3),Z=4,R=0.0519,wR=0.1035。Ⅲ属单斜晶系,P2_1/c空间群,晶胞参数a=1.0280(5)nm,b=1.2113(5)nm,c=1.9192(7)nm,β=93.560(7)°,V=2.1366(16)nm~3,D_c=1.712g·cm~(-3),Z=4。Ⅳ属单斜晶系,Cc空间群,晶胞参数a=1.5875(7)nm,b=1.0359(5)nm,C=2.1919(9)nm,β=101.266(8)°,V=3.535(3)nm~3,Dc=1.443g·cm~(-3),Z=4。Ⅰ和Ⅱ为两核铁簇,其簇骨架Fe_2PCl和Fe_2P_2呈蝶状。Ⅲ和Ⅳ     

两个具有松散配位的三核钼簇合物{Mo_3(μ_3—S)(μ—S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}·CH_3CN(Ⅰ){Mo_3(μ_3—O)(μ—S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}(Ⅱ)的合成和晶体结构

本文报道了两个具有松散配位的三核钼簇合物{Mo_3(μ_3—S)(μ—S)_3[S_2P(OEt)_2]_4·(C_3H_3ON)}·CH_3GN(Ⅰ)、{Mo_3(μ_3—O)(μ—S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}(Ⅱ)的合成和晶体结构。簇合物(Ⅰ)属单斜晶系,空间群为P2_2/n,晶胞参数为a=16.579(3),b=16.959(2),c=16.867(2);β=94.44(1)°;v=4728 3;Z=4;D_c=1.778g·cm~(-3),用Patterson法解出结构,最终偏离因子R=0.045。簇合物(Ⅱ)属三斜晶系,空间群为P1,晶胞参数为a=13.175(4),b=13.372(6),c=16.656(3);α=117.87(4)°,β=60.09(3)°,γ=109.03(3)°;ν=2231 3;Z=2;D_c=1.798g·cm~(-3),用直接法解出结构,最终偏离因子R=0.066。两个簇合物均为以具有一个松散配位为特征的单帽三核簇,而且松散配位上均被一嘿唑五员环所占据,其主要差别在于簇合物(Ⅰ)的簇胳为Mo_3S_4,而簇合物(Ⅱ)则为一Mo_3OS_3·文中对这一“松散”配位的三核钼簇合物的活泼性进行了讨论。     

Mo-Ag类立方烷异四核簇[Mo~2Ag~2S~4](TDT)~2(PPh~3)~2的合成, 结构表征和反应性

采用[2 1 1]的设计合成模式,以二核化合物[Mo_2S_4(TDT)_2](Me_4N)_2(1,TDT=S_2C_6H_3CH_3~(2-))为起始物,与Ag(PPh_3)_3(NO_3)反应,首次合成[Mo_2Ag_2S_4](TDT)_2(PPh_3)_2CH_2Cl_2(2)的类立方烷异四核簇合物.文中报道了该化合物的晶体结构、红外光谱、紫外可见光谱和电化学研究结果,以此簇合物和过量的Cu(PPh_3)_2dtP[dtP=S_2P(OEt)_2]反应发现金属Ag可被Cu取代,形成其同系物[Mo_2Cu_2S_4](TDT)_2(PPh_3)_2,这是迄今研究较少的原子簇反应类型.化合物的结晶学参数如下:单斜晶系,空间群:P2_1/n,晶胞参数:a=1.7202(4)nm,b=1.7632(3)nm,c=1.9033(8)nm,β=99.24(3)°,V=5.698(3)nm~3,Z=4,D_c=1.69g/cm~3,对于6158个衍射,最终结构偏离因子R=0.040,R_W=0.048.     

四核银簇合物Ag_4(o-CH_3C_6H_4CS_2)_4(Py)_4与二核铜化合物Cu_2(o-CH_3C_6H_4CSS_2)_2(Py)_2的合成和晶体结构

邻甲基苯荒酸四乙基铵盐分别与硝酸银和氯化铜反应,经毗啶重结晶,得到四核银簇合物Ag_4(o-CH_3C_6H_4CS_2)_4(Py)_4(晶体Ⅰ)和二核铜化合物Cu_2(o-CH_3-C_6H_4CSS_2)_2(Py)_(晶体Ⅱ)。用X射线单晶衍射法测定了它们的晶体结构。晶体Ⅰ的空间群为P2/n。晶胞参数:a=14.757(4),b=12.231(3),c=15.183(4)A,β=91.14(2)°,V=2739.95A~3,Z=2。2590个衍射点参与修正,最终偏差因子R=0.087。晶体Ⅱ的空间群为C_1~1-P1。晶胞参数:a=9.307(7),b=9.546(7),c=10.119(8)A,α=95.06(9),β=109.74(10),γ=118.86(10)°,V=705.94A~3,Z=1。1198个衍射点参与修正,最终偏差因子R=0.086。 Ag_4(o-CH_3C_6H_4CS_2)_4(Py)_4分子中Ag_4呈蝴蝶状构型,其配位情况与四核银簇合物Ag_4(a-C_(10)H_7CS_2)_4(Py)_4相似。Cu_2(o-CH_3C_6H_4CSS_2)_2(Py)_2分子构型与Cu_2(a-C_(10)H_7CSS_2)_2(Py)_2十分相似。Cu—Cu键长为2.608A。而且邻甲基苯荒酸与Cu~(2+)反应包括一个氧化还原反应,也与a-萘荒酸与Cu~(2+)反应相似。可以认为邻甲基苯荒酸与a-萘荒酸有相似的空间效应和电子效应。     

簇合物[Fe_6S_9(SCH_2CH_2OH)Cl]~(4-)的合成、结构和性质研究

将一定量的FeCl_2,(NH_4)_2MoS_4和HSCH_2CH_2OH在甲醇-甲醇钠溶剂中反应,制备出[(C_2H_5)_4N]_4[Fe_6S_9(SCH_2CH_2OH)Cl]单晶。该化合物属三斜晶系,P1空间群,a=12.818(4),b=13.622(3),c=18.328(7),α=106.09(2)°,β=100.75(2)°,γ=102.69(2)°,Z=2。对7517个可观测反射(1>3σ(Ⅰ))精修所有结构参数,得到一致性因子R=0.0818。结构测定结果表明:在[Fe_6S_9(SCH_2CH_2OH)Cl]~(4-)中存在着μ_2—S桥,μ_3—S桥和μ_4—S桥。该簇合物的核[Fe_6S_9]~(2-)由8个非共面的菱形组成。其中有4个Fe(μ_2—S)(μ_3—S)Fe,2个Fe(μ_2—S)(μ_4—S)Fe和2个Fe(μ_3—S)(μ_4—S)Fe菱形。用EHMO方法对簇合物电子结构进行了量子化学的研究。结构上键长表现出Fe—(μ_4—S)>Fe—(μ_3—S)>Fe—(μ_2—S)的规律,与EHMO计算得到键序Fe(μ_4—S)相似文献   

STUDIES OF SYNTHESIS, STRUCTURE AND PROPERTIES OF CLUSTER COMPOUND [Fe_6S_9(SCH_2CH_2OH)Cl]~(4-)

By mixing appropriate quantity of FeCl_2, (NH_4)_2MoS_4 ano HSCH_2CH_2OH in MeOH--MeONa, the crystal [(C_2H_5)_4N]_4[Fe_6S_9(SCH_2CH_2OH)Cl] was obtained. The cluster compound crystallizes in triclinic, space gtoup, P1, and crystal cell constants:a = 12.818(4)A, b = 13.632(3)A, c = 18.328(7)A, α = 106.09(2)°, β = 100.75(2)°, γ = 102.69(2)°, Z = 2. On the basis of 7517 unique data (I>3σ(I)) the structure has been refined toR = 0.0818 by the block-diagonal least-squares. The result of structure analysis shows thatthe cluster compound [Fe_6S_9(SCH_2CH_2OH)CI]~(4-) includes doubly bridging μ_2-S, triply bridgingμ_3-S and quadruply bridging μ_4-S. The [Fe_6S_9]~(2-) core of [Fe_6S_9(SCH_2CH_2OH)CI]~(4-) consistsof eight nonplanar Fe_2S_3 rhombs that are fused edge-sharing to give four Fe(μ_2-S)(μ_3-S)Fe,two Fe(μ_2--S)(μ_4-S)Fe and two Fe(μ_3-S) (μ_4-S)Fe subunits. The quantum chemical calcu-lation of EHMO method was carried out for this cluster compound. The structure analysisgives a rule wit     

Studies on solid state reactions of coordination compounds——XLⅦ.Solid state syntheses and crystal structures of cluster compounds {Cu_3MoS_3I}(PPh_3)_3S and {Cu_3WS_3Br} (PPh_3)_3S

Reactions of [NH_4]_2[MS_4](M=Mo,W),CuX(X=Br,I)and PPh_3 in the solid state producedfour mixed-metal sulfur containing clusters{Cu_3MS_3X}(PPh_3)_3S(M=Mo,W;X=Br,I),two of which(1:M=Mo,X=I;2:M=W,X=Br)were structurally determined.Crystals of 1 and 2 are triclinic,space group P(1:a=11.895(3),b=13.107(1),c=20.473(2),α=74.95(6),β=84.87(8),γ=64.27(7)°,Z=2,V=2776.1 ,Rw=0.064 for 6443 observed reflections.2:α=11.876 (1),b=13.065 (2),c=20.325(2),α=74.95(1),β=85.39(1),γ=64.09(1)°,Z=2,V=2737.3,R_w=0.055 for 5303 observedreflections).The results of the structure determination showed that the central units of the two cubane-like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alter-nate comers.The differences of cubane-like cluster compounds obtained from solid state reactions andfrom solution reactions are discussed.     

双三苯膦铁硫原子簇合物(μ-n-C_4H_9S)(μ-CH_3OCOCH_2CH_2S)Fe_2(CO)_4(PPh_3)_2的合成及晶体结构

通过(μ-BrMgS)(μ-n-C_4H_9S)Fe_2(CO)_6与CH_2=共轭加成及中间物的醇解反应先制得(μ-n-C_4H_9S)(μ-)Fe_2(CO)_6,然后进一步将它同PPh_3反应制得标题配合物,该簇合物晶体属C2/c空间群,α=30.892(4),b=12.454(2),c=25.725(4);β=91.46(1)°,Z=8;Dc=1.284 g/cm~3;R=0.060,其簇核由2个铁原子和2个硫原子构成蝶式结构,2个三苯膦配体处于铁—铁变键反位,2个桥硫原子上的取代基团均以e键与硫原子相连。