SYNTHESIS AND STRUCTURE OF[Et_4N]_3[FE_3(SPh)_3Br_3Cl_3]

<正> The title compound was synthesized and its structure solved. The formula is [Et4N]3[Fe3(SPh)3Br3Cl3]. M=1231.95, monoclinic, space group C2/c, a=24.569(4), b=13.504(2), c=18.348.(3)A, β=110.78(1)°, V=5691(3)A3, Z=4, Dm= 1.41, Dc=1.44-g/cm3. The flat structure of the anion has. a planar [Fe3S3] ring and three phenyl groups. Statistical distribution of chlorine and bromine atoms on two sides of the [Fe3S3] plane results in a C2 symmetry of the anion.     

CRYSTAL AND MOLECULAR STRUCTURE OF β-(Et_4N)_3 [Fe_3(SPh)_3Br_3C1_3]

<正> Introduction. Previously, we have reported the compound α-(Et_4N)_3[Fe_3(SPh)_3-Br_3Cl_3](Ⅰ)~1 with C_2 symmetry. An isomer(Ⅱ) of this compound, which has D_3dsymmetry, is reported in this paper. Brow-green crystals of Ⅱ is obtained from the reaction of FeCl_2, PhSNa and Et_4NBr (1:1:1) in acetonitrile solution.     

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     

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-     

Preparation,Characterization and Thermal Decomposition Kinetics of the Complexes [Dy(p-NBA)_3Phen]_2·3H_2O and [Dy(m-NBA)_3Phen]_2·4H_2O

The title complexes [Dy(p-NBA)3Phen]2·3H2O(I) and [Dy(m-NBA)3Phen]2·4H2O(Ⅱ) were synthesized, in the two molecular formulas of which NBA is nitrobenzoate and Phen is 1,10-phenanthroline. The characterizations of the complexes were carried out by means of elemental analysis, UV, IR, XRD and molar conductivity. The thermal decomposition of the two complexes were studied under the non-isothermal condition by DSC, TG-DTG and IR methods in detail. The kinetic parameters of the dehydration process were also obtai...     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_2[S_2P(OEt)_2]_3][SOP(OEt)_2](0)_2

<正> M=1140.85, monoclinic, P21/c. a=12.748(2), b=14.320(2), c=23.118 (3)A,β=101.07(1)°, V=4141(2)A3, Z=4, Dc=1.830 g.cm-3. Final R=0.039 for 4160 reflections.The title compound is a rather irregular trinuclear molybdenum cluster having only two M-M bonds with two shorter Mo-Mo distances of 2.808(1), 2.839(1), and one longer Mo-Mo distance of 3.337(1)8. The existence of two Mo-Mo bonds is coincident with the electron counting for {Mo3} cluster core, and may be regarded as a result of the oxidation of a compound Mo3(μ3-S)(μ-S)2 (μ-L)[S2P(OEt)2]4(L') (L'=neutral ligands)1 characterized by us previously.     

THE SYNTHESIS AND STRUCTURE OF THE CLUSTER COMPOUND {(Mo_3(μ_3-O)(S_2)_3[S_2P(OEt)a]3)2Cl}FeCl_4

<正> INTRODUCTION. Resently a series of M2-type trinuclear Mo clusters with the formula {Mo_3(μ-Y)(S_2)_3[S_2P(OEt)_2]_2]_3}X, (Y=O or S; X=Cl or I) have been synthesized by our research group through either the reduction of the higher valence Mo(V) compounds or the oxidation of the middle valence Mo(Ⅲ) species. In this paper we report a novel type of cluster cation     

Structures, energy bands and conductivities of (Me_3NEt)[Pd(dmit)_2]_2 and (NEt_4)[Pd(dmit)_2]_2

The electrical conductive molecular crystals (Me3NEt)[Pd(dmit)2]2 and (NEt4)[Pd (dmit)2]2 (dmit = 4,5-dimercapto-1,3-dithiole-2-thione) have been prepared, and their crystal structures and conductivity-temperature curves have been determined. The fact that the conductivity at room temperature of (Me3NEt)[Pd(dmit)2]2 (a = 58 Ω· cm-1) is much higher than that of (NEt4)-[Pd(dmit)2]2(cr= 2.2 Q~1 ?cm'1) has been rationally explained by the results of energy band calculations. (MeNEt3)[Pd(dmit)2]2 belongs to monoclinic system, P21/m space group and (NEt4)[Pd (dmit)2]2 belongs to triclinic system, P1 space group. The structural conducting component of the crystals is the planar coordinative anion [Pd(dmit)2]05- which forms the face-to-face dimmer [Pd(dmit)2]2-. These dimers have been further constructed to be a kind of two-dimensional (2-D)conductive molecular sheet by means of S…S intermolecular interactions. The tiny difference of the above 2-D molecular sheets of the two title crystals has resulted in one     

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.     

CRYSTAL STRUCTURE OF ORGANOLANTHANIDE COMPLEX [Li~+(DME)_3]_2[(CpNd)_4(μ_2-CH_3)_2(μ_4-O)(μ_2-Cl)_6]~(2-)

<正> The crystal and molecular structure of [Li+(DME)3]2[(CpNd)4 (μ2-CH3)2(μ4-O) (μ2-Cl)6]2~was determined from single crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P21/n with lattice parameters a= 14. 614(5), b= 18. 683 (5),c= 24. 595 (6) A, β = ,91-85(2)°, V = 6712(3) A3,2 = 4,DC = 1. 63g/cm3,F(000) = 3256,Mr=1650. 85. The structure was solved by direct methods and Fourier techniques and refined by least-squares to a final R=0. 047,RW = 0. 049 for 3761 with I>3σ(I). The result revealed that the anion [(CpNd)4(μ4-O) (μ2-Cl)6(μ2-CH3)2]2- is composed of four neodymium (Ⅲ) atoms bridged by six Cl atoms, two methyl groups and one oxygen atom, and every Nd is bonded to a cyclopentadienyl group. The four Nd atoms form a distorted tetrahedron. The cations are composed of two Li+(DME)3 with average Li-O distance of 2. 120(40) A.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF (QH)_3[Mo_2O_4(■-COO)(NCS)_4]·H_20 AND (QH)_3[Mo_2O_4(CH_30H)(NCS)_5]

<正> INTRODUCTION. In the reported crystal structures of di(μ-X)(X=O,S)-bridged oxodimolybdates (Ⅴ), the local, symmetric array of donor atoms linked to the Mo atoms is well known. The title compounds (QH)_3[Mo_2O_4(COO)-(NCS)_4]-H_2O(Ⅰ) and (QH)_3[Mo_2O_4(CH_3OH)(NCS)_5](Ⅱ), in which the environments     

CRYSTAL AND MOLECULAR STRUCTURE OF TRIS(TRIPHENYLPHOSPHINE) TRI-CARBONYL-BRIDGED TRIPLATINUM CLUSTER COMPOUND Pt_3(μ2-CO)_3(Ph_3P)_3

<正> PRELIMINARY INFORMATION. The title compound, is one of the products synthesized by a reaction of bis(triphenylphosphine)-platinum, carbon monoxide and chlorine gas in sodium hydrate solution at room temperature. An X-ray structural analysis has been undertaken to clarify unambiguously the arrangement of ligands around the triangle platinum cluster core. This has been     

CRYSTAL STRUCTURE OF {Mo_3(μ_3-S)(μ-S)_3 [S_2P(OEt}_2]_4·PhCH_2CN}

<正> Mr=2548.12, Triclinic, P1, a=15.941(5), b=15.957(2),c=20.240(6)A, α=76.41(2),β=83.87(2),γ=74.41(2)°,V=4814.6A3, Z=4, Dc=1.757g.cm-3, Final R=0.053 for 11867 reflections. There are two crystallographically independent M1 type trinuclear Mo cluster molecules with 'loose coordination site', A and B, in an asymmetric unit of the title crystal. They are formulated as {Mo3S4(u-dtp)(dtp)3.PhCH2CN}(dtp=[S2P(OEt)2]-) and have essentially identical cluster molecular configuration, but differ from each other in the conformations for the phenyl rings of the ligands PhCH2CN. The lengths of the Mo-Mo bonds are 2.750(1), 2.753(1),and 2.768(1)A for molecule A and 2.742(1), 2.756(1), and 2.764(1)A for molecule B, while the dihedral angles betweem the phenyl ring and the {Mo3} triangle are 25.0° and 94.9° for A and B respectively.     

A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

PREPARATION AND STRUCTURAL CHARACTERIZATION OF [Cd(2-SC_5H_3NH-3-SiMe_3)I_2]_2

<正> Reaction of cadmium iodide (CdI2) with 3-(trimethylsilyl)-pyri-dine-2-thiol(TSPT ) in methanol yields the title compound. The dimeric complex C16-H26NzSi2S2I4Cdz crystallizes in the monoclinic system, space group P21/n, a = 7. 712 (3), b = 24. 55(1), c = 8. 170(1) A,β=95.86(2)°, V = 1539(2) A3, Mr=1099. 12, Z = 2, F(000) =1008, μ= 55.65cm~1,Dc = 2. 37gcm-3, final R = 0. 046 and Rw = 0. 052 for 1066 observed unique reflections. The molecule with [Cd2I4]0 core has a center symmetry and the TSPT ligand is present as monodentate donor in the neutral thione form , protonated at the pyridine nitrogen. The existence of this structure may be rationalized on the basis of intermolecular hydrogen bonding between the NH proton of the ligand and the terminal iodine atom of the adjacent molecules.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)_2(μ-Cl)_3[S_2P(OEt)_2]_3

<正> M=1013.98, hexagonal, P63/m, a=b=15.492(2), c=8.530(4)A, γ=120°, V=1773A3, Z=2, Dc=1.899°g.cm-3. Final R=0.042 for 611 reflections.This is a Bl(bicapped) type trinuclear molybdenum cluster with two S capping atoms located on the 63 axis and exhibits full D3h symmetry. The Mo-Mo distances are 2.606(1)A, with a bond order of 11/3. It is paramagnetic.     

THE STRUCTURE AND SYNTHESIS OF [MoFe_3S_4(Etadtc)·_5]MeCN

<正> INTRODUCTION. More and more models of active center were suggested with wide study on the MoFe-protain and FeMo-cofactor of nitrogenase. Most of them contain MFe_3S_(3+4) (M=Mo,Fe) cubane-type core, so a great interest has been focused on the Studies of MoFe_4, cubane-type compounds. The type species have been reported by holm et al. We have also made researches on the single cubane-like compounds. Here we describe the synthesis and structure of [MoFe_3S_4(Et_2dtc)_5MeCN (1).     

Crystal structure and single crystal EPR of (NH_4)_2(15-crown-5)_3[Cu(mnt)_2] and (NH_4)_2(benzo-15-crown-5)_4[Cu(mnt)_2]·0.5H_2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2? anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(II) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

STUDY ON STRUCTURE OF SULFUR-BRIDGED TRANSITION METAL CLUSTERS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3 [Mo_3(μ_3-S)_2 (μ_2-Cl)_3Cl_6]

The compound (C_5H_7S_2)_3[Mo_3 (μ_3--S)_2 (μ_2--Cl)_3 Cl_6] forms dark black octahedralcrystals with the following crystallographic parameters: a=22.885(10)A, c=25.407(7)A. Thespace group is I4_1/α, Z=16, ρ_(obs.)=2.073g/cm~3, ρ_(calc.)=2.126g/cm~3. The 1621 independentreflections with I≥3σ were collected on a CAD-4 four-circle diffractometer by means of MoK_αradiation. The structure was solved by three-dimensional Patterson synthesis and refined byleast squares technique to a final discrepancy factor of R=0.056. The results of our investiga-tion reveal that the molecule consists of a trinuclear Mo cluster anion and three planar mono-cations.surrounding the cluster anion. As the core of the anion the triad of Mo atoms, possessing anequilateral triangular configuration, is linked by two μ3--S bridging atoms and three μ2--Clatoms. Besides, two terminal Cl atoms are attached to each Mo atom to form an octahedralconfiguration. The diamagnetism and the short Mo-Mo distances (2.556 A, 2.641 A, 2.653 A)clearly indicate the existence of Mo-Mo bonds. The anion as a whole has an idealized D_(3h) localsymmetry.     

SYNTHESIS, CHARACTERIZATION AND STRUCTURE OF [Co(DBP)_2·3Py]_2·2CHCl_3

The mixed ligand complex of cobalt with dibutylphosphate (HDBP) and pyridine has been synthesized. Elemental analysis yields the result that the formula of this compound is Co(DBP)_2·3Py·CHCl_3 (Py=pyridine). The thermal analsyis, visible spectra and magnetic properties of it have been studied as well. Single crystal structural analysis shows that the crystal is triclinic with space group P and the unit cell parameters are as follows:a=14.490(10), α=90.37(4)°,b=15.721(7), β=96.04(5)°,c=20.109(12), γ=105.63(4)°.The final R factor is 0.0773. Two Co atoms are connected by two bridging DBP groups to form a dinuclear molecule [Co(DBP)_2·3Py]_2 which has a C_s, symmetry. Each cell contains two dinuclear molecules and four chloroform molecules. The cobalt is coordinated in an octahedral arrangement by three oxygen atoms and three nitrogen atoms, of which one oxygen atom comes from a monodentate DBP group, two oxygen atoms from two bridging DBP groups, and the three nitrogen atoms from the three pyridi