MoFe_3S_4单立方烷自兜合成及(Et_4 N)(MoFe_3S(Et_2dtc)_5]·MeCN的晶体结构

<正> 具有MoFe_3S_4单立方烷簇骼的化合物与固氮酶的钼铁蛋白及铁钼辅基存在着某些类似性,从而引起人们的极大注意。1973年卢嘉锡提出的固氮酶活性中心模型—福州模型(Ⅰ)—就具有网兜状缺口MoFe_3S_3单立方烷结构。迄今,还没有见到用简单化合物一步合成,即所谓自兜(Spontaneous self-assembly)合成单立方烷的报导。     

MOFe_3单立方烷原子簇研究 Ⅰ.(Et_4N)[MoFe_3S_4(Et_2NCSS)_5]CH_3CN的自兜合成及结构

双齿含硫配位体,二乙胺基二硫代甲酸钠盐与氯化亚铁及四硫代钼酸铵在二甲基甲酰胺溶液中,经一步自兜反应得到(Et_4N)[MoFe_3S_4(Et_2NCSS)_5]CH_3CN(1).X射线单晶结构测定表明1具有类立方烷骨架,核心价态为[MoFe_3S_4]~(4+),通过对1的阴离子结构分析,指出配位基的双齿螯合作用对化合物的稳定性及结构的影响.化学键理论计算也解释了阴离子中的主要键长特点.     

新型V_2Ag_2S_4类立方烷簇合物(Et_4N)_2·[V_2Ag_2S_4(OC_4H_8dtc)_2(PhS)_2]的合成与结构

一个新型的V_2Ag_2S_4异金属立方烷簇合物从包含(NH_4)_3VS_4,Ag(PPh_3)_2NO_3,OC_4H_8dtcNa以及PhSNa的自兜反应体系中分离。标题化合物的晶体属单斜晶系,空间群C2/c,a=20.448(3),b=15.086(2),c=17.923(2),β=109.32°。用1500个I>3σ(I)的衍射数据进行精修,R=0.068。化合物中金属表观价态为Ⅴ(Ⅳ)与Cu(Ⅰ)。结构特点表明存在着从Ag(Ⅰ)到Ⅴ(Ⅳ)的部分电子转移。另讨论了反应体系中各物料的作用和可能的形成机理。     

MoFe_3S_4单立方烷原子簇研究 Ⅲ.三核链状簇合物向单立方烷簇合物的转化及MoFe_3S_4(Et_2NCS_2)_5·CH_3CN的结构

以Fe(DMF)_6[(FeCl_2)_2MoS_4]与Et_2NCS_2Na在DMF中反应实现了三核链状簇骼向单立方烷簇骼的转化,得到了MoFe_3S_4(Et_2NCS_2)_5并测定了它的晶体结构.本文指出与配体有关的氧化还原过程及配体的配位特点对这一转化反应及其产物的影响,同时比较了由于核心氧化态的差异而造成的簇骼结构面貌的变化.     

MoFe_3S_4(S_2CNC_4H_8)_5和WFe_3S_4(S_2CNC_4H_8)_5单立方烷簇合物的快原子轰击质谱研究

本文报道了标题簇合物的快原子轰击质谱(FAB—MS)研究,提出了标题簇合物质谱的可能断裂途径及其结构相关性。指出标题簇合物的FAB—MS与电子轰击谱(EI—MS)所表现的两种迥然不同的断裂模式。观察到单立方烷缺一个顶点和缺二个顶点的碎片离子如[WFe_2S_3(S_2CNC_4H_8)_2]~+、(MoFe_2S_3(S_2CNC_4H_8)_3]~+和[WFeS_3(S_2CNC_4H_8)_3]~+、[MoFe_3S_3(S_2CNC_4H_8)_2]~+等,而后者的簇芯(MoFe_3S_3)结构具有缺口的立方烷状构型特点,是目前合成工作者期待合成但尚未合成出的一种固氮模型物。     

铁钼硫原子簇化合物的合成与结构研究 Ⅴ.[MoFe_3S_4]类立方烷簇合物的转化反应和[Et_4N]_3[Mo_2Fe_6S_8(SC_6H_4CH_(3-m))_3Cl_6]的晶体结构

具[MoFe_3S_4]类立方烷结构单元的双类立方烷化合物[Et_4N]_4[Mo_2Fe_7S_8(SR)_(12)](1a,R=Ph;1b,R=tolyl-m)或单类立方烷化合物[MoFe_3S_4(dtcR_2)_5](2a,R=Me;2b,R=Et)与酰氯在乙腈中反应,分别得到不含Fe桥的双类立方烷化合物(Et_4N)_3[Mo_2Fe_6S_8(SR)_3Cl_6](3a,R=Ph;3b,R=tolyl-m)与[MoFe_3S_4]骨架支解后的Fe(dtcR_2)_2Cl(4a,R=Me;4b,R=Et)。说明在相同反应条件下,[MoFe_3S_4]单元在1中比在2中稳定。本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及~1H NMR谱的证实。本文报道3b的单晶结构及3的~1H NMR数据。3b属六方晶系,P6_3/m,a=1.6827(3),c=1.5951(16)nm;V=3.91158nm~3;D_c=1.491g/cm~3;Z=2;F(000)=1780;偏离因子R=0.048。化合物2与酰氯反应产生4,由红外及紫外可见光谱证实。     

Structures that should be Described in Higher-Symmetry, Centrosymmetric Space Groups. Part 1. The Disordered Structures of [(CH_3CH_2)_4N]_3{[(SCH_2CH_2S)MoS_3]_2Fe}, [(CH_3CH_2)_4N]_2{[S_2CN(C_2H_5)_2]_4Fe_4S_4} and [(CH_3CH_2)_4N]_3{[(SCH_2C

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SYNTHESIS AND STRUCTURE OF (Et_4N) [Fe_4S_4 (Et_2NCS_2)_4 ]

<正> INTRODUCTION. The Fe_4S_4 cubane-like clusters have been extensively studied as the model compounds for the active center of the Fe-S proteins in the last fifteen years. Coucouvains et al. have recently reported the syntheses and structures of a few Fe_4S_4 cluster compounds containing R_2NCS_2(R_2dtc) and RS (or Cl) mixed terminal ligands and having [Fe_4S_4]~(2+) core oxi-     

[(CH_3)_4N]_2Na[Mo_2O(S_2)_3S_5]·H_2O的合成和晶体结构

标题晶体属斜方晶系,空间群Pbn2_1,a=9.086(2),b=13.439(3),c=22.858(11),V=2791,Z=4,Dc=1.927g/cm~3。在CAD—4衍射仪上收集强度数据,采用直接法和Fourier技术解出结构,并用全矩降最小二乘法修正。对于1180个独立衍射最终偏离因子0.067。结构中的阴离子与其同系物[(CH_3)_4-N]_2K(Mo_2O(S_2)_3(NO)_2]·H_2O中的阴离子配位情况相似。只是结构中的Mo—S与Mo—O键长有差异。这种差异在两者的红外光谱上有着相应的表现。     

MoFe_3S_4单立方烷原子簇研究Ⅱ.MoFe_3S_4 (C_5H_(10)NCSS)_5的合成与结构

六氢吡啶基二硫代甲酸钠盐、氯化亚铁及四硫代钼酸铵在二甲基甲酰胺及二氯甲烷中,经一步自兜反应,分别得到了[MoFe_3S_4(C_5H_(10)NCSS)_5]DMF及[MoFe_3S_4(C_5H_(10)NCSS)_5]CH_2Cl_2。通过X射线衍射测定了后者的晶体结构,比较了它与[MoFe_3S_4(Et_2NCSS)_5]~-结构特点的异同,同时研究了反应物摩尔比对产物的影响以及溶剂分子的置换反应。     

Synthesis and Structural Characterization of a Hetcrobimctallic Molybdenum-Copper-Sulfur Compound [Et_4N]_2 CMoCu_3S_4 (S_2CNEt_2)_3]

<正> The title compound crystallizes in orthogonal space group P212121with α= 12. 848 (5), b =13. 227 (3), c = 29. 519(8) A ,Z = 4 , V= 5016. 5 A3 and Dc = 1. 483g/cm3. 4940 independent reflcctiions were collected on a CAD4 diffractometer with MoKa radiation in the range of 1°<0<25°,of which 3559 reflections having intensities I >3σ(I) were used for structure determination. The structure was solved by direct methods and refined by the least-squares method to final discrepancy factors R=0. 071 and Rw - 0. 075. The anion of the title compound can be described as a slightly distorted MoS42-tetrahedron coordinated by three [CuS2CNEt2] units ,with the four metal atoms lying approximately in a plane.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A TUNGSTEN-COPPER-SULFUR CLUSTER [Et_4N]_2[WCU_3S_4(S_2CNEt_2)_3]

<正> [Et4N]2 [WCu3S4 (S2CNEt2)3], Mr = 1172. 01, orthorhombic, space group P212121 with a=12. 858(9),b=13. 204(5) ,c=29. 501(9) A ,V=5008. 7 A3, Z = 4, Dc = 1. 55gcm-3, μ(MoKa) = 40. 3cm-1. The final R and Rw are 0. 069 and 0. 075, respectively, for 3072 observed unique reflections. The anion contains a slightly distorted WS42~ tetrahedron coordinated by three CuS2 CNEt2 units,with four metal atoms lying in a plane.     

MoFe_3S_4单立方烷原子簇研究 Ⅳ.新型的双跨桥六配体单立方烷簇合物 MoFe_3S_4(μ-Me_2NCS_2)_2(Me_2NCS_2)_4·2CH_3 CN 的合成与结构

在二甲胺基二硫代甲酸钠、氯化亚铁及四硫代钼酸铵的自兜反应体系中,以分步结晶法分离出MoFe_3S_4(Me_2NCS_2)_5·CH_2Cl_2及 MoFe_3S_4(Me_2NCS_2)_6·2CH_3CN 等单立方烷簇合物,并测定了后者的结构.它的分子含两个 Me_2NCS_2桥,并具有最高核心氧化态[MoFe_3S_4]~(6+).本文报道该化合物的结构特点,指出在自兜反应体系中,可能存在几种不同氧化态的单立方烷原子簇化合物.     

Synthesis of [MoOS_3Cu_3I(3, 5-diMePy)_4]·CH_3CN and (Et_4N)_4[Mo_4Cu_8O_4S_(12){(Ph_2PS)_2N}_4] from Solid State Product [Et_4N] _4[Mo_2O_2S_6Cu_6I_4Br_2]

Awell－groundmixtureof犤NH４犦２犤MoS２O２犦,CuI,andEt４NBr,wasputintoareactiontubeandheatedat８０℃for４hunderanitrogenatmosphere．AfterextractingtheresultantblacksolidwithCH３CN,theextractwasfilteredtoaffordadeepredfiltratewhichcontainsatwin－nestshapeinter－mediate犤NEt４犦４犤Mo２O２S６Cu６I４Br２犦１犤１犦．Twin－nestshapeproductsareinterestingbecausetheirbridgegroupscleavagecanincorporatedifferentligandsintotheclusterspecieswithinterestingskeletalstructures．Takingadvantageo…     

Crystal Structure of [Et_4N][Sm(S_2CNEt_2)_4]

The crystal structure of .[Et4N][Sm(S2CNEt2)4] was determined by X-ray diffraction technique. The crystal crystallizes in monoclinic system, space group P21/n with a= 1. 1695(3), b=2.0821(6), c=1.7420(7) nm, β=99. 79(3)°? Z=4, Dc= 1. 39 g/ cm3, μ(Mo/KTσ) = 18. 4 cm-1, F(000) = 1812. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R of 0. 053 for 3116 (Ⅰ> 3σ- (Ⅰ)) reflections. Each asymmetric unit contains two ions [Sm (S2CNEt2)4]-1 and [Et4N] +1, having distance between central atoms N5 and Sm3+ to be 0. 6522 nm. The atom Sm is coordinated by eight sulphur atoms. The Sm-S distance lies in the range of 0. 285-0. 290 nm with an average of 0. 288 nm.     

MASS SPBCTRA OF CUBAN-LIKE CLUSTER COMPOUND [MoFe_3S_4 (S_2CN■)_5]

<正> INTRODUCTION. We have previously reported the mass spectra of a single MoFe_3S_4 cubane-like cluster compound (Et_4N)MoFe_3S_4(Et_2NCS_2)_5. Its analogue MoFe_3S_4(C_4HaNCS_2)_5 having the same core structure has rently been synthesized and characterized structurally. In this paper, the results of its mass spectra investigation using an electron impact (EI) ionization mass spectrometer are offered and identified by metastable technique, isotopic     

Synthesis and structure of a novel MoFe_4S_4 cubane-like cluster (Me_3PhCH_2N)_2[MoFe_4S_4(SC_6H_(11))_7]

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CRYSTAL STRUCTURE OF (Et_4N)_3[Mo_2Fe_6S_8(SPH)_9]

<正> Introduction. A series Of Mo-Fe-S complexes with doublecubane structure has been synthesized and identified. Because of the similarity of its extended X-ray absorption fine structure (EXAFS) to that of FeMo cofactor and nitrogenase, suggestion has been made that the doublecubane complexes may serve as models for the Mo site of nitrogenase. Therefore, the investigation of this type of complexes has attracted much attention. By using the similar method of spontaeous self-assembly reaction, and starting from certain kinds of Mo-Fe-S compounds, we have been able to obtain several kinds of compounds, one of which     

含全螯合配位体的类立方烷型簇合物[(C_2H_5)_4N]_2{Fe_4S_4[S_2CN(C_2H_5)_2]_4}的合成、结构、性质及量化计算

在无氧无水和纯净氮气保护下,以FeCl_2,(NH_4)_2WS_4,NaS_2CN(C_2H_5)_2和(C_2H_5)_4NBr为原料,合成出了簇合物[(C_2H_5)_4N]_2{Fe_4S_4[S_2CN(C_2H_5)_2]_4}。其晶体属单斜晶系,Cc空间群,a=22.125(6),b=11.313(3),c=25.053(8);β=118.05(2),V=5534.2,Z=4。它具有类立方烷型核心Fe_4S_4,每个Fe原子上都有一个双硫螯合配位体S_2CN(C_2H_5)_2。Mssbauer谱、X光电子能谱及量子化学计算结果都表明,簇合物中含有两种数量相等而价态不同的Fe。提出了该簇合物生成反应的图解,报道了簇合物的红外光谱、紫外-可见光谱及氧化还原性质。     

FORMATION AND CRYSTAL STRUCTURE OF (Et_4N)_2[Fe(SC_6H_4CH_3-P)_4]

<正> INTRODUCTION. In the study of synthetic methods and chemical reactions of Mo-Fe-S cluster compounds for simulation of the catalytic active center of nitrogenase, the reaction.systems of MoS_4~(2-) and varios ferric or ferrous salts have caused the interests of many chemists. We have been studying the system of ferrous thiolates and thiomolybdates and found interesting results. In a previous paper, we reported the syn-