SYNTHESIS AND STRUCTURE OF A NEW DINUCLEAR MOLYBDENUM(O) COMPLEX [Et_4N]_2 [Mo_2 (CO)_8 (SCH_2COOEt)_2]

<正> t Reaction of Et^NI, NaSCH2COOEt with Mo(CO)6 in MeCN affords a new dinuclear molybdenum(O) complex, [Eti,N]2 [Mo2(CO) 8(SCH2COOEt)2] (I) . The crystal and molecular structure has been determined from three-dimensional X-ray data. 1_ crystallizes in the triclinic, space group PI with a=10.362(1), b= 10.391(1), c=10.815(2) X, a=91.64(2), 6=100.07(2), Y=H4.46(1)? Z=l, R= 0.048 for 2975 reflections with I?o(I). Noribonding of Mo...Mo distance (3.939(11)A) in _! supports the previous speculation for the two-electron redox properity,of complex anion, [Mo2(CO)g(SR)2J2~.     

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.     

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-     

PENTACOORDINATED IRON-SULFUR COMPLEXES I.SYNTHESIS AND STRUCTURE OF DINUCLEAR COMPLEX [Fe_2(o-SC_6H_4S-S,S')_4](Et_4N)_2

<正> INTRODUCTION. On close investigation of the 'P cluster' of nitrogenase, which is known to consist of Fe_4S_4~(2+) core, scientists have considered that the collective properties are highly suggestive of those being variants of analogue Fe_4S_4~(2+) clusters. Attention has been directed recently to the possibility that 'P cluster' variations may include some or all Fe atoms that are not 4-coordinated as in usual Fe-S analogues but are 5-coordinated.     

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.     

THE MOLECULAR AND CRYSTAL STRUCTURE OF [Et4N]2[Fe2S2（NO）4]

<正> The compound [Et_4N]_2[Fe_2S_2(NO)_4] (M_r=556.36) crystallizes in the monoclinic,space group P 2_1/n with a=9. 688(3), b=10. 882(2), c=12. 625(2), β=97. 86(3)°, Z=2, V=1318. 4, D_c=1. 40g/cm~3, ;μ(MoK_a)=12. 8cm~(-1) and F(000)=588. The final R=0. 028 and R_w=0. 029 for 2041 reflections (I≥3σ(I)).The crystals of [Et_4N]_2[Fe_2S_2(NO)_4] consist of discrete cations [Et_4N]~+ and anions     

CRYSTAL STRUCTURE OF (Et_4N)_4[Mo_2Fe_7S_8(SPh)_(12)]

<正> (Et4N)4[Mo2Fe7S8(SPh)12] : Mw=2670.3, triclinic, p1, a=12.775(4), b=13.076(3), c=20.576(4)A, α=80.00(2), β=81.39(2), γ=61.51(2)°, V=2966.3(14) A3, Z=1, D=1.494 gcm-3, R=0.077 for 4031 observed reflections. The complex was prepared by reactions of (Et4N)2[Fe4(SPh) 10] with (Et4N)2MoS4 in an ace-tonitrile solution. The structure of [Mo2Fe7S8(SPh)12]4- anion is a double-cubane-like configuration bridged by a Fe(SPh)6 group.     

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 STRUCTURE OF A NEW LINEAR TETRANUCLEAR Mo-Fe-S CLUSTER (Et_4N)_2[(Et_2NCSSMoS_2)_2O_3Fe_2S_2]·DMF

<正> (Et4N)2[Et2NCSSMoS2)2O3Fe2S2]·DMF(1) ,Mr= 1174. 10,mono-clinic,space group P21/n,a = 9. 608(3),b=17. 962(2),c=15. 312(3) A ,β=95. 03 (3)°,V=2632. 4 A3,Dc= 1. 48 g/cm3 and Z=2. The structure was solved from 2499 reflections with I>3σ(Ⅰ) and refined by full-matrix least squares method to R(Rw) = 0. 073(0. 087). The anion of 1 has linear Mo -Fe -Fe-Mo array. The oxidation states of metal atoms in this cluster are 2Mo(Ⅵ) + 2Fe(Ⅲ).     

STRUCTURE OF [Et4N]2[Mo2（CO）8（SCH2C6H4CH2SH）]

<正> Mr =1015.05, P21/c, a= 10.912(4), b= 12.088(3), c= 18.807(8) A.β=103.57(3)° ,V= 2411.4 A3, Z = 2, DC = 1.40 g/cm3.λ(MoKα)= 0.71073 A, μ=7.2 cm-1,F(000)=1048.Room temperature, final R=0.069, Rw=0.091. The geometry around the Mo atom is a distorted octahedron. The equatorial Mo-C distances are shorter than the axial ones. The Mo...Mo distance is 3.949A.     

EPR AND ELECTRONIC STRUCTURE OF Mo(V) COMPLEX Mo_2O_3(S_2CNEt_2)_4

<正> INTRODUCTION. Particular interest of some chemists has directed to the chemistry of molybdenum, as the oxidation states of molybdenum (-2～+6) are interesting and Mo atom in various forms usually is contained in the active site of enzymes or catalysts.     

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     

双核钼铁硫簇合物[Fe(2,2’-联吡啶_3)][(S_2MoS_2FeCl_2]的合成与晶体结构

双核Mo-Fe-S原子簇配合物[Fe(2,2′-bpy)_3][S_2MoS_2FeCl_2],是(Et_4N)_2MoS_4、FeCl_2和2,2′-联吡啶在乙腈中反应得到的结晶化合物.晶体属单斜晶系,空间群P2_1/c;a=9.328(3),b=26.788(2),c=13.764(3)(?);β=95.38(3)°;V=3424.2(11)(?)~3;Z=4;D_c=1.698g/cm~3;F(000)=1752.晶体结构用直按法解出;经全矩阵最小二乘法修正,最后R=0.068,R_ω=0.071(3933个I>3(?)(I)的独立衍射).在晶体结构中配位阴离子[S_2MoS_2FeCl_2]~(2-)是排布在阳离子[Fe(2,2′-bpy)_3]~(2+)所形成的空腔中.它是以非统计分布的形式存在,从而较准确地测定了各项键参数.Mo…Fe距离为2.773(2)(?),Mo-S_b和Fe-S_b有大致相等的键长.     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

CRYSTAL AND MOLECULAR STRUCTURE OF A OINUCLEAR MOLYBDENUM(O) CARBONYL COMPLEX WITH THIOLATO-BRIDGES,[Et_4N]_2(Mo_2(CO)_8(SC_sH_4OH)_2-C~2]

<正> The structure of a dinuclear Mo(0) carbonyl complex with thiolato bridges, [Et4N]2 [Mo2 (CO)8(SC6H4OH)2-CR](1), Mr =926.82, was determined from three-dimensional X-ray data.1 crystallizes in the triclinic,space group P1,a= 9.534(1),b=10.094(1),c= 11.954(1)A;α=80.93(38),β=68.62 (31),γ= 83.06(33)°;Z=1; V = 1055.4A3,Dc=1.46 gcm-3;A = 0.035, R2= 0.046,F(000)=476. The configuration of planar MoS2Mo core center of 1 with Mo-S distance of 2.617A and No...Mo distance of 4.0722 A is nearly the same as that of the Sph-analog. This provides an example to demonstrate the ineffectiveness of electrophilic feature of R ligand on the MoS2Mo core in a series of dinuclear Mo(0) complexes with thiolato-bridges.     

CRYSTAL STRUCTURES OF [Bu4N]2[M2Ag3（ μ3—S）2（μ—S）4S2Et2dtc]（M=W,Mo）

<正> The title compounds were prepared from the reation of (NH4)2MS4 (M=W,Mo),AgNO3,NadtcEt2 and Et4NBr in CH3CN-H2O solution. The isomorphous compounds [Bu4N]2[W2Ag3S8Et2du] ( I ) and [Bu4N]2[Mo2Ag3S8Et2dtc] (Ⅱ) crystallize in triclinic space qroup Pi with the following crystal parameters:α=13. 043(4),b = 21. 640(6),c=10. 757(6)A ,α=95. 09(5),β = 91. 90(4),γ = 98. 57(3)°,Z = 2,V = 2987A3,Dc=1. 76g/cm3 for I 5;a= 12. 989(2) ,b=21. 574 (9) ,c= 10. 7/1(1) A .α= 95. 06(7), β=91. 61(4), γ=98. 52(2)°, Z = 2,V = 2961 A3.Dc= 1. 58g/cm3 for Ⅱ . The final R and Rw values are 0. 061 and 0. 072 for Ⅰ ,and 0. 062 and 0. 076 for Ⅱ The M2Ag3 (M = W, Mo) unit in anion M2Ag3S8Et2dtc forms a five-membered ring.     

四核钼簇合物的配体取代反应及产物Mo_4S_4(μ-OAc)_2(dtp)_4的晶体结构

标题化合物(Ⅰ)经由Mo_4S_4(μ-dtp)_4(Ⅱ)[dtp=S_2P(OEt)_2]和Ni(OAc)_2反应而得。(Ⅰ)晶体属单斜晶系,空间群P2/c,a=13.176(4),b=11.699(3),c=18.526(4)(?),β=116.11(3)°,V=2564(3)(?)~3,Z=2,D_c=1.776g·cm~(-3)。晶体结构由直接法解出,最终偏离因子R=0.085。本文结果表明,可由已知的四核钼簇合物经过配体置换反应,合成得到其簇骼中心[Mo_4S_4]保持不变并具有-OAc作为桥式配体和-dtp作为端基配体的混合配体类立方烷[Mo_4S_4]簇合物。     

SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_20_2S_2(Py)_4(Mo0_4)

<正> Introduction. A series of trinuclear molybdenum clusters has been synthesized and identified. Most of them have almost the sameMo-Mo distance. We have synthesized another kind of trinuclear molybdenum complex which has different Mo-Mo distances and can be comsidered as composed of the complex (Mo_2O_2S_2(py)_4)~2+ and the molbdenic ion (MoO_4)~2-. This paper reports the synthesis and structure of the title compound.     

SYNTHESIS AND CRYSTAL STRUCTURE OF THE TRI-(μ2-METHOXY)-BRIDGED 'DOUBLE-CUBANE' CLUSTER COMPLEX (Et_4N)_3[Mo_2Fe_6S_8(OMe)_3(SPh)_6]

<正> The title compound was synthesized and crystal structure was solved. (Et4N)3[Mo2Fe6S8(OMe)3(SPh)6], Mr=1922.39, hexagonal, PGs/m, a = 17.750(3), c=15.880(2) A, V=4332.7(26) A3, Z-2, Dx=1.477 g/cm3, MoKα, λ= 0.71069 A, R = 0.059, Rw = 0.065, for 814 observed reflexions. The complex anion contains two Fe3MoS4 cubane-like units linked throug their molybdenum atoms by three ,μ2-methoxy-groups, and the overall structure of the anion has C3b symmetry.     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.