SYNTHESIS AND STRUTURE OF THE FIRST INTERSTITIAL μ_7-S CLUSTER Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12)

The reaction of Co_2(CO)_8 with EtSPCl_2 gives a new crystal like compound Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12),whose structure has been determined by single crystal x-ray diffraction.This special com-pound reveals some new features in cluster chemistry~1:The fragmentation of a ligand precursor EtSPCl_2 yieldsthree kinds of fragments,μ_7-S,μ_4-PSEt and μ-SEt,which are ligands in the same cluster molecule.There is anew type of bridging S presented——A μ_7-S atom is interspaced into seven Co core.     

SUBSTITUTION REACTION OF LIGANDS IN TRINUCLEAR Mo CLUSTERS WITH "LOOSE COORDINATION SITE" AS WELL AS SYN-THESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-S) (μ-S)_3(dtp)_3(C_3H_4N_2)_3 (dtp)·(CH_3)_2CO

When trinuclear molybdenum cluster compound with "loose coordination site", Mo_3(μ_3-S)(μ-S)_3(μ-dtp)(dtp)_3·H_2O(A) (dtp=diethyldithiophos-phinato anion), is reacted with an excess of imidazole, the H_2O ligand and the bidentate bridging ligand μ-dtp are found to be simultaneously substituted by the imidazole to form the title compound. The title crystal belongs to the space group P(?), Z =2, with the following unit cell parameters: a=14.465(2), b=14.653(4), c=14.886(6), α=99.36(3),β=93.11(2),γ=114.29(2),V=2812(3). The crystalline compound consists of an ordered array of the cluster cation and dtp anion with acetone as packed molecule. The cation possesses a symmetry of C_3. Three Mo atoms form basically an equilateral triangle with three Mo—Mo bond lengths of 2.763 (1), 2.762(1), 2.756(1) respectively.     

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.     

CRYSTAL STRUCTURE OF TRINUCLEAR MOLYBDENUM CLUS-TER Mo_3(μ_3-S)(μ_2-S_2)_3(Et_2dtc)_3I SYNTHESIZED BY SOLID STATE REACTION

<正> The title cluster compound was synthesized by solid state reaction at low heating temperature. C15H30IMo3N3S13, Mr=1083. 93, monoclinic, P21/n, a = 14.396(3), b = 13. 116(3), c=18. 142(8)A;β= 91. 36(3)°; V =3425(2)A3, Z = 4. Dc = 2. 10g/cm3, F(000) = 2112,μ(MoKa) = 27. 29cm-1, final R = 0. 034, Rw = 0. 051 for 1845 unique observed reflections (I≥3σ(I)). The three Mo atoms form an equilateral triangle with an average side length of 2. 714 A. Each Mo atom is coordinated with seven S atoms forming a distorted pentagonal bipyramid. The iodine atom connects with three S atoms (out of the CMo3] plane) with an average distance of 3. 205 A.The title compound has similar cubane-like cluster core [Mo3S7I] as the compound Mo3(μ3-S)(μ2-S2)3(dtp)3I(dtp= (EtO)2PS2).     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3[Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]

The space group of the title crystal is Pnam. The unit cell parameters are: a=17.226(4), b=14.306(7), c=15.074(4); z=4, Dobs=2.03g·cm~(-3), D_(calc)=2.063g·cm~(-3). The crystal structure was solved by the heavy atom method and refined by the full-matrix least-squares until the final conventional discrepancy factor was reduced to 0.068. The results of the investigation show that the crystal consists of trinuclear Mo cluster anions [Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]~(3-) together with planar (C_5H_7S_2)~ monocations, surrounding the cluster anions. In the cluster anion three Mo atoms, forming a nearly equilateral triangle (2.755(1), 2.755(1), 2.743(1)), are bound by a μ_3-S bridging atom, while each pair of Mo atoms is bridged further by a μ_2-S_2 ligand. Besides, each Mo atom is coordinated to two terminal Cl atoms, so that the coordination sphere of each Mo atom approaches closely a pentagonal bipyramid. In addition, a single Gl atom, not at all involved in the coordination spheres of the three Mo atom     

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.     

A CLUSTER COMPOUND WITH DI-ENDOXYGEN LIGANDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF [Fe(MOS_4O)_2][N(C_2H_5)_4]3

[Fe(MoS_4O)_2] [N(C_2H_3)_4]_3 cluster compound with di-end-oxygen ligands has been prepared and characterized by the X-ray diffraction method. The compound crystallizes in a monoclinic space group P2_1/n with lattice parameters a=13.019(4), b=16.959(5), c=18.234(5), β=97.34(2)(°), Z=4. The final agreement factors are R=0.0740, Rw=0.0598. The terminal bond length, Mo-S_t and bridged one, MO-S_b for the compound are much longer than the counterpart without end-oxygen ligand. It possibly suggests that low valence of molybdenum and smaller electronegativity of sulphur than oxygen lead to the charge transfer as S→Mo→O.     

CRYSTAL AND MOLECULAR STRUCTURE OF μ-ACYL Fe-S COMPLEX (μ-C_2H_5S)[μ-CO-C(CH_3 )=CH_2]Fe_2(CO)_6

<正> The crystal and molecular structure of(u-C2H5S)[μ-CO-C(CH3)-CH2]Fe2(CO)6, Mr = 409.958 has been determined by X-ray diffraction method. Crystals of this complex are monoclinic, belonging to space group P21/c, and the cell parameters are a = 9.191(1), b = 9.666(1), c = 18.47(2)A,β=98.71(1)° V= 1621.9A3,Z=4,Dc=1.68g/cm3.Thg final R and Rw equal 0.058 and 0.089 for 1948 observed unique reflections. The acyl and ethyl-thio groups are bridged to two iron atoms to form an envelope type of structure. The bond lengths of Fe(1)-0(1), Fe(2)-C(1), Fe(l)-S, Fe(2)-S, Fe(l)-Fe(2) involved in the envelope structure are 1.992, 1.980, 2.260, 2.242 and 2.552A, respectively.     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF A NOVEL MOLYBDENUM-COPPER-SULFUR CLUSTER COMPOUND [(CH_3CH_2 )_4N]_2 [(μs-S)CusS_6(S_2)_6Mo_6O_6].DMF

The synthesis and crystal structure of a novel molybdenum-copper cluster compound with [(μs-S)Cus] core is reported. It was prepared from Cu2Br2 upon reaction with molybdenum sulfur compound [CH3CH2)4N]2[Mo2O2S2-(S2)(S4)]. The title compound crystallizes in the monoclinic system space group Cc with cell dimensions: a=21.320(5), b=21.869(3), c=13.029(5)A,β=118.28(1)°,Z=4, V=5349A3 and Dc=2.48 g.m-3. The structure has been determined by Patterson and Fourier methods and then refined by the least squares method to a final R of 0.053. There are some distortions from octahedron in configuration of the [(μs-S)Cu6]6 core with three weak Cu-Cu bonds.     

SYNTHESIS AND CRYSTAL STRUCTURE OFμ-TEREPHTHALATO BINUCLEAR COBALT(Ⅱ) COMPLEX [Co_2(tpha)(bpy)_4](ClO_4)_2

<正> The structure of μ-terephthalato binuclear cobalt (Ⅱ) complex CCo2(tpha)(bpy)4](ClO4)2(tpha=μ-terephthalato, bpy=2,2' -bipyridine) has been determined by X-ray method. Crystals of title complex are monoelinic, space group P21/c, with a = 13. 086(2), b = 9. 428(2), c=20. 237(4) A. β= 108. 83(1)°, Mr = 1105.61, Z = 2, Dx = 1. 55g/cm3, μ= 8. 09cm-1 and F(000)= 1128. The structure has been solved by direct methods and refined to R=0. 053, The title cation has Ct symmetry in which the terephthalato group acts as bridging ligand between the two metal atoms. Each cobalt(Ⅱ)ion is in a distorted octahedral environment. The Co.....Co distance is 10. 35A.     

Synthesis and Liquid Crystal Behaviors of 2,4-Dioxo-3-pentyl 4-decyloxy Cinnamate Rhodium （I） Complexes

The title complexes have been synthesized by the reaction of [RhCI(CO)2]2 or [RhCI(COD)]2 (COD = 1,5-cyclooctadiene)with the organic ligand 2,4-dioxo-3-pentyl 4-decyloxy cinnamate 2. The complex 3 based on dicarbonylrhodium(I) shows nematic phase, while the complex 4 containing rhodium(I) bound to a COD ligand is a nonmesogen. The relationship between molecular structures and liquid crystal behavior has also been discussed by means of computer-aided molecular modeling.     

SYNTHESIS AND SPECTRAL STUDIES OF(μ-PHENYLTHIO) (μ-ALKYLTHIO) HEXACARBONYLDIIRON COMPLEXES

Through reductive reaction between PhL1 and μ-S2 Fe (CO/6,tollowed by nucleophilicsubstitution of the intermediate (μ-PhS} (μ-LIS} Fe2 (CO)6 toward RX,nine Fe-S clus-ter complexes of (μ-PhS)(μ-RS)Fe2(CO)6 series have been synthesized.The influence of RX structures on the activities in nucleophilic substitution has been examined and possible steroisomers and isomer ratios of the complexes determined.In addition,the regular variations of isomer's CH3-S and CH2-S which are caused by the anisotropic effects of C-O and orientations of unshared electron pairs on sulfurs,have also been preliminarily discussed.     

Coordination chemistry of organometallic polydentate ligand Reactive chemistry of the tridentate ligand trans-Fe(Ph_2PQu-P)_2- (CO)_3 [Ph_2PQu=2-diphenyl-phosphino-4-methylquinoline] and molecular structure of [Fe(CO)_3(μ-Ph_2PQu)_2HgI]~ [HgI_3]~-

Reaction of a new type of bidentate ligand PhPQu [ PhPQu = 2-diphenylphosphino-4-methylquinoline] with Fe(CO)5 in bu-tanol gave trans-Fe(PhPQu-P)(CO)3 (1).Compound 1,which can act as a neutral tridentate organometallic ligand,was reacted with I B,II B metal compounds and a rhodium complex to give six binuclear complexes with Fe-M bonds,Fe(CO)3(u-Ph2PQu)MXn(2-7) [M=Zn(Ⅰ),Cd(Ⅱ),Hg(Ⅱ),Cu(Ⅰ),Ag(Ⅰ),Rh(Ⅰ)],and an ion-pair complex [Fe(CO)3(n-Ph2PQu)2HgI][HgI3]- (8).The structure of 8 was determined by X-ray crystallography.Complex 8 crystallizes in the space group P-1 with a=1.0758(3),b= 1.6210(4),c = 1.7155(4) nm; a = 75.60(2)β=71.81(2),Y = 81.78(2) and Z = 2 and its structure was refined to give agreement factors of R =0.050 and Rw = 0.057.The Fe-Hg bond distance is 0.2536 nm.     

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     

STRUCTURE OF A Fe-S CLUSTER COMPLEX [{(μ-PhCH_2S)Fe_2(CO)_6}_2(μ4-S)]

<正> [{(μ-PhCH2S)Fe2(CO)6}2(u4-S)], Mr = 837.95, triclinic, Pl,a=13.701(3),b=16.542(5), c=17.030(5)A,α=107.69(2),β=90.15(2),γ= 114.49(2)°,V=3309.3A3, Z=4, Dx=1.68 g/cm3,MoKa,λ=0.71069A μ=20.2 cm-1,F(000)=2008, room temperature, final R=0.035 for 4960 independent reflections. The molecule possesses approximate C2 symmetry with the pseudo-twofold axis passing through the unique sulfur atom u4-S(2) and the midpoint of the other two u2-sulfur atoms S(1) and S(3). The unique u4-sulfur atom has a tetrahedral geometry and donates its six valence electrons to the four iron atoms. The average Fe-(μ4-S) distance of 2.247 A is slightly shorter than the average Fe-(μ2-S) distance of 2.265A.     

CRYSTAL STRUCTURE OF MIXED-METAL CLUSTER (η~5-C_5H_5)_2W_2Fe_2(μ_3-S)_2(CO)_8

<正> (η5-C5H5)W2Fe2(μ3-S)2(CO)8,Mr = 897. 80,monoclinic,C2/c,a= 18. 019 (2),b = 8. 330(1),c= 16. 043(2) A ,β= 114. 30(1)°,v = 2194. 7(6)A3,z= 4, Dx = 2. 717g/cm3, A(MoKa) = 0. 71037 A , μ= 122. 01cm-1, F (000) = 1656, T = 295K,R=0.056,Rw = 0. 059 for 1250 observed reflections. The crystals of the title compound are isomorphous with the analog (η5-C5H5)2Mo2Fe2(μ3-S)2(CO)8.     

A new route to prepare the mixed oxo-ethylidynecapped trinuclear tungsten(Ⅳ)cluster and the crystal structure of H_2Na_3[W_3O(CCH_3)(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5H_2O

The synthesis and the structural characterization of the title compound H_2Na_3[W_3O(CCH_3)-(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5 H_2O are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtained by Zn dust reduction of Na_2WO_4·2H_2O in acetic anhydride.The title compound has been characterized by X-ray diffraction,UV/VIS and ~1H NMR spectra.The tungsten atoms in the cluster cation and anion are in the oxidation states of W(IV)and W(VI)respectively.The crystal is rhombohedral with the space group R32,a=17.058(3),c=49.665(9),γ=120°,V=12516(9)~3,Z=6,final R=0.037 for 2071 reflections with I≥3σ(I).Boththe cluster cation and anion have a C_3 symmetry.The important interatomic distances in angstroms forthe cluster cation are:W—W,2.730(2);W—μ_3-O,2.00;W—O(carboxyl),2.12;W—O_t,2.18(2).     

Synthesis,Structure, and Luminescent Property of a 3-D Strontium Complex [Sr_3(pda)_2(Hpda)_2(H2O)_2]_n·2nH_2O

The title complex [Sr3(pda)2(Hpda)2(H2O)2]n·2nH2O(H2pda = pyridine-2,6-dicar- boxylic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 10.3795(8), b = 9.2225(7), c = 18.5726(14) , β = 104.377(2)o, V = 1722.2(2) 3, C28H22N4O20Sr3, Mr = 997.36, Z = 2, Dc = 1.923 g/cm3, μ = 4.722 mm-1, F(000) = 984, the final R = 0.0269 and wR = 0.0538. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by carboxylate groups. The luminescent property of the title complex has been investigated.     

The Crystal and Electronic Structure of A Reticular Type Mo-Fe-S Cluster Compound [Et_4N]_4[Mo2Fe_4S_9(SCH_2CH_2S)_2]

The single crystal of [Et4N]4 [MO2Fe4S9(SCH2CH2S)2] was obtainedby reaction of (NH4)2HoS4, FeCl3 , HSCH2CH2SH and Et4 NBr in CH3CN and MeOH-MeONa. Cluster compound [Et4N]4 [Mo2Fe4S9(SCH2CH2S)2] crystal -Lized in the monoclinic space group C2/c with unit cell parameters:a = 17. 672(2)A, b = 33. 851(4)A, c = l3. 900(3)A, β=135.11(4)°, V=5868.8 (3.9)A3 and Z = 4. On the basis of 3514 unique data (I>2σ(I)) the structure was refined to R = 0.0575. The anion [Mo2Fe4S9(SCH2CH2S)2]4-of the cluster compound includes doubly bridging (μ2-S), triply bridging (μ3-S) and quadruply bridging (μ4 -S) . The structrue analysis gives a rule with bond lengths decreasing in the order of Fe-(μ4-S)> Fe-(μ3-s)> Fe-(μ2 -s) and EHMO calculation gives the other rule with bond order increasing in the order of Fe-(μ4-S)< Fe-(μ3-S)相似文献