REACTIVITY OF METAL(O) DITHIOCARBAMATO CARBONYL COMPLEXES [Mo(CO)_4(S_2CNEt_2)]~- (M=Mo, W): SYNTHESIS AND STRUCTURE OF A NEW MIXED-VALENCE DINUCLEAR MOLYBDENUM-SULFUR COMPLEX, [Et_4N]_2[(CO)_4MoS_2MoS_2]

<正> The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group Pbom with a = 18.403(2), b = 11.963(1), c= 13. 482(1)(?) , Z = 4, V = 2986(?)3, Dc=1. 55g/cm3, Mr = 6S2. 69. R =0. 042 and Rw =0. 057 for 1975 independent reflections with I≥3σ(I), F(000) = 1416, μ =11. 2cm-1. The structure of the anion of 1 consists of an octahedron for the lowvalent Mo atom and a tetrahedron for the high-valent Mo atom sharing an S - S edge. The Mo - Mo bond distance is 2. 992 (2) (?) and the bimetallic center MoS2Mo is planar with Mo-S of 2. 517 and 2. 231 A and MoSMo angles of 78. 04° and 77. 67°. The electron delocalization between the two Mo atoms with wide separated oxidation states is also discussed.     

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.     

THE CRYSTAL STRUCTURE OF TR1S (μ-SULFJDO)-(U3-SULFJDO)-TETRAKTS (O,O-DIETHYLPHOSPHORODITHIOATO-S,S)-OXAZOLE-TRI-MOLYBDENUM-ANTIMONOUSCHLORID {Mo_3(U3-S)[u-S)_3·SbCl_3][S_2P(OEt)_2]_4·(C_3H_3ON)}

<正> Mr = 1445.67, triclinic. The space group is P1 with the unit cell parameters: a = 10.342(3), b = 11.994(3), c = 21.352(4) A; (?)= 76.27(2), β - 88.55(2)°, r = 73.26(2)°; V = 246lA3, Z = 2, DC = 1.959 g.cm-3. The final R factor is 0.068 based on 4053 reflectioons with I≥3(?)(Ⅰ). The title compound may be regarded as the result of that a molecule of trinuclear Mo cluster {Mo3S4[S2P(OEt)2]4·(C3H3ON)}[1] connects with a molecule of SbCl3 by three bridging S atoms. The skeleton {Mo3SbS4} is a distorted cube. The distances of Mo-Mo bonds are 2.728(2), 2,743(2) and 2.751(2) A, respectively, and the distances between Sb and Mo atoms are 3.814(2), 3.815(2) and 3.847(2) A, respectively.     

Synthesis,structure and electrochemistry of dithiocarbamato phenthiolate oxo-molybdenum(Ⅳ)complexes[MoO(SΦ)_2(S_2CNEt_2)]

The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]~- with phenthiolate [Et_4N]SΦin acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com-plex [MoO(SΦ)_2(S_2CNEt_2)]~-,which crystallizes in two forms of crystals,[Et_4N][MoO(SΦ)_2(S_2CNEt_2)](1a) and [Et_4N][MoO(SΦ)_2(S_2CNEt_2)]·(CH_3)_2CHOH (1b).The structures of1a and 1b were determined from three-dimensional X-ray data.1a crystallizes in the mo-noclinie,space group C_c with a=12.321(4),b=15.245(4),c=16.087(9);β=98.44(4)°.V=2989~3,Z=4,D_c=1.35 g/cm~3 and R=0.031 for 2434 reflections [I>3(I)].1b crystallizes inthe monoclinic,space group P2_1/n with a=9.861(1),b=20.357(3),c=17.122(5)A;β=92.27(2)°,V=3434.3~3,Z=4;D_c=1.29 g/cm~3 and R=0.051 for 2852 independeut reflections [I>3σ(I)],The structures of 1a and 1b reveal that the anion [MoO(SΦ)_2(S_2CNEt_2)]~- contains asingle oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atomis a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linkedto oxo group by a hydrogen-bond of 1.928A,leading to the increase of Mo=O bond distance(1.718).Mo—S distances are 2.44 and 2,39.The electrochemical behavior of 1 wasdiscussed also.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF A CUBANE-LIKE MOLYBDENUM-COPPER-SULFUR CLUSTER {Mo3CuS4[S2P(OC2H5)2]3(I)(μ-CCl3(00)CH3CN}

<正> The synthesis and crystal structure of the cubane-like cluste with [Mo3CuS4] core is reported herein. The title compound crystallizes i triclinic space group Pl with the following unit cell dimensions: a 11.723(3), b = 14.353(6), c = 15.533(4)A;α= 75.40(3)°,β=69.13(2)°,γ 64.93(3)°; Z = 2; V = 2196 A3; DC = 2.033 g·cm-3.7704 independent reflec tions were collected on CAM four-circle diffractoneter with MoKa radiatio in the range of 1 < <25°, with only 2083 reflections having intensitie I > 3σ(I). The structure was determined by direct methods and refined b the least-squares method to a final R index of 0.091. There are some distortion in the cubane-like [Mo3CuS4] core, with three Mo-Mo bonds and thre weak Mo-Cu bonds.     

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.     

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.     

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 A LINEAR TETRANUCLEAR Mo-Fe-S CLUSTER, (Et_4N)_4C(MoS_4)_2Fe_2S_2D·(CH_3OH)_2

<正> C_34H_88O_2N_4Mo_2Fe_2S_10, Mt= 1209. 25,monoclinic, P2_1/a,a= 17. 722 (7) ,b= 11. 857(5),c= 13. 743(5) A .β= 112. 29 (3)°, V= 2672. 0A3,Z = 2,Dc = 1. 503 g·cm-33,μ(Moka) = 14. 0 cm-1,T=193 K. Final R=0. 045 for 1943 observed reflections (I≥3σ(I)). In the anion [(MoS4)_2Fe2S2]4- ,the two Fe atoms, each attached with a chelating MoS42- unit, are bridged by two sulfur atoms. The metal atoms are arranged in a linear fashion with Mo-Fe-Fe angle of 179. 1(1)°, and Fe-Fe and Fe-Mo distances of 2. 746(2) and 2. 801(2) A, respectively. The long Fe-S distances (average 2. 246A) in Fe2S2 ring could be a result of the hydrogen-bonding interaction between the sulfur atom and the methanolic hydrogen atom.     

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.     

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 AND MOLECULAR STRUCTURE OF TETRACHLORO-BIS[BIS(2-ETHYLHEXYL)-SULFIDE]-PLATINUM(IV)

<正> C32H68Cl4S2Pt, Pt[(BEHS)2Cl4], Mr=853.9, space group P21/a, a =10.445(3), b=15.012(4), c = 13.506(5) A,β=101.43(3)°,V=2076(1) A3, Z=2, DC=1.37 g·cm-3, MoKa radiation, u= 39.3 cm-1, F(OOO) = 876 e, R = 0.053 for 1790 reflections. Pt(IV) is coordinated by four chloro atoms and two S atoms of BEHS, forming a somewhat distorted octahedron with Pt-S of 2.366 and Pt-Cl of 2.309A. The packing pattern of the long BEHS chain may allow the existence of conformational disorder.     

Synthesis and Crystal Structure of Complex {[Cu(N-men)_2(cda)_2]·[Cu(N-men)_2]·(ClO_4)_2}(N-men=N-Methylethylenediamine,cda=Carbamyldicyanomethanide Anion)

<正>Mononuclear complex {[Cu(N-men)2(cda)2]·[Cu(N-men)2]-(ClO4)2} was synthesized by sodium carbamyldicyanomethanide Na(cda), N-methylethylenediamine and hydrate copper perchlorate. The crystal belongs to the triclinic system, space group P 1 with a = 7.229(2), b = 8.114(2), c = 15.936(4) A, α = 80.511(4), β = 78.993(4), r= 72.118(4)°, V = 867.6(3) A3, Z = 1, C20H44Cl2Cu2N14O10, Mr = 838.68, Dc = 1.605 g/cm3, F(000) = 434 and μ = 1.449 mm-1. The structure was refined to R = 0.0480 and wR = 0.1289 for 2503 observed reflections (I > 2σ(I)). In the complex there exist two kinds of coordination models for Cu (II) ions. One is that the Cu (II) ion is coordinated by four nitrogen atoms which are from two N-men molecules, and a slightly distorted square planar coordinate environment is formed around the Cu (II) ion; the other is that the Cu (II) ion is coordinated by six nitrogen atoms, of which four are from two N-men molecules and the left from nitrile groups, resulting in a distorted octahedron around the     

Vanadium(Ⅳ)dimer complexes containing [V(o-C_6H_4OS)_3]~(2-)fragment and caged sodium ions

Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A=Ph_4P~+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared bythe reaction of anhydrous VCl_3 and Na_2mp in the molar ratio 1:3.Complex(3)(A=Et,N~+,L=L'=MeOH)was prepared by the reaction of VCl_3,Na_2mp and Li_2S in the molar ratio 1:2:1.The com-plexes were characterized by X-ray diffraction crystallography,infrared spectra,magnetic suseepti-bility,and cyclic voltammetric measurements.Complex 2 crystallizes in the triclinic space groupP1 with a=12.813(6),b=14.199(4),c=12.790(5),α=112.72(2),β=104.24(4).γ=88.68(4)°,V=2073.6,and Z=1.The structure was refined to R=0.058.Complex 3 crystallizes in the mono-clinic space group P2_1/n with a=12.359(3),b=17.452(6),c=14.829(13),β=96.51(5)°,V=3177.8,and Z=2.The final R factor is 0.067.Both of the anions of 2 and 3 contain two[V(rap)3]~(2-) fragmentslinked by sodium ions through the μ_3-O bridges with a crystallographic center of symmetry.The V(IV)atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.     

SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-O)(μ-S)_3[S_2P(OEt)_2]_4(C_3H_3N_2)

<正> Mr=1164, space group C2/c, a=14.954(13)A,b=22.323(6)A,c=27.003(18)A,β=98.23(7)°,V=8920 A3, Z=8. Final R=0.069 for 2818 unique diffraction data with I≥30(I). The title cluster compound is of Ml configuration with a triple bridging atom O and with a 'loosely coordinated site' occupied by an imidazole ligand. Three Mo-Mo bond lengths are 2.657 (2), 2.649(2),and 2.646(2)A,respectively. The average bond length of Mo-(μ3-O) bonds is 2.052 A.     

SYNTHESIS AND CRYSTAL STRUCTURE OF THE LANTHANIDE COMPLEX WITH MIXED LIGANDS [Pr (CH_3COO)_2(NO_3)(Phen)]_2

<正> [Pr(CH3COO)2(NO3)(Phen)]2, Mr = 1002. 41. The crystal is monoclinic, space group I2/m, with a = 11. 725(5), b = 12. 269(5), c=12. 732(4) A, V = 1792(2)A3,β=101. 88(0)°. Z = 2, Dc=1. 86g/cm3,μ(MoKa) = 27. 5cm-1, F (000) = 984. The structure was solved by Patterson method and Fourier syntheses, and refined by full matrix least-squares method to R = 0. 033 for 1660 observed reflections with I>3σ(I). The molecule of the complex is a dimer and each praseodymium atom is eight-coordinated in a distorted square antiprism geometry.     

SYNTHESIS AND CRYSTAL STRUCTURE OF {C(η~5-C_5H_5)_4Nd_4(μ_4-O) (μ_2-Cl)_8)]·[Li(dme)_2THF]_2

<正> The reaction of (η5-C5H5)3Nd·THF and NdCl3·2LiCl·nTHF in solution at room temperature gave rise to[(η5-C5H5)4Nd4(μ4-O)(μ2-Cl)8][Li(dme)2THF]2 (Mr = 1654.44). Crystals of the compound were obtained at about - 10℃. The intensity data were collected under nitrogen atmosphere at-60℃. The crystal belongs to the rhombic system with space group Pna21 and the unit cell parameters : a=19. 010(7),b = 23. 231(6) ,c= 14. 180(4) A ;V = 6261. 91 (A3) , DC= 1. 67 (g/cm3), λ(MoKa) = 0. 71069A,F(000) = 3240,μ(mm-1) = 3. 660;Z = 4. Least-squares refinement with anisotropic temperature factors for all non-hydrogen atoms led to the final R=0. 054, Rw = 0. 056. The molecule is made up of the anion group and the cation. The oxygen atom links four Nd3+together as μ4-bridge. The eight chlorine atoms form the eight chlorine-bridge bonds among four Nd3+ions. The average bond length is : Nd-O=2. 374,Nd-Cl = 2. 811,Nd-C=2. 777,Nd(a)- Nd(b) = 3. 872A.The bond angles of Nd(a) -Nd (b)-Nd(c) fall in the range of 62~63°,th     

STRUCTURE OF [W(H)_2(F)(OH_2)(PMe_2)_4]F

<正> Mr = 546.3, orthorhombic, space group Cmc21, a = 14.223(4), b = 12.907(3), c = 12.343(4) A, V = 2265.746 A3, Z = 4, DC = 1.601 Mg.m-3, λ= 0.7106 A, μ(MoK(?)) = 56.86 cm-1, F(OOO) = 1048. Final R = 0.044 for 1937 observed reflections. Cation [W(H)2(F)(OH2)(PMes)4]4 has a mirror symmetry, an equatorial belt of four PMe3 groups and mutually syn fluoride and water Ugands. The mean W-P length is 2.462 (A) and P-C 1.83 (A). From the dimensions of the metal, fluoride and water system ( W(1)-F(1) = 2.08(1), W(1)-0(1) - 2.084(9), F(2)-O(1) = 2.59(2) A and F(2)-W(1)-O(1) - 76.7(4)°) an in-terligand hydrogen bond was assumed. The ligand water molecule also makes an H-bonded contact with the fluoride counter ion.     

Synthesis and Structure of a New Dinuclear Molybdenum(Ⅰ)Compound with Cyclohexanthiolate Ligand,[Mo_2(SC_6H_(11)_2(CO)_8]

<正>Molybdenum( I )-compound [Mo2(SC6H11)2(CO)8] 1, crystallizes in monoclinic, space group P21/c with a = 9.5863(9), b = 9.4469(9), c = 13.869(1) A, β = 99.697(2)°, V= 1238.1(2) A3, Z = 2,DC= 1.734 g/cm3, μ = 12.23 cm-1 and F(000) = 644. The finalR = 0.0455 and wR = 0.1159 for 1590 observed reflections with I> 2σ(I). 1 possesses a rhombic bimetallic core MoS2Mo with the Mo-Mo bond length of 2.975(1) and Mo-S of 2.485(2) A.     

THE CRYSTAL STRUCTURE OF A NOVEL TETRANUCLEAR SILVER CLUSTER COMPLEX Ag_4(α-C_(10)H_7CS_2)_4(Py)_4·2Py

The title compound has been synthesized by the reaction of α-dithionaphthoic acidwith AgNO_3 in an organic solvent. The single crystals were obtained by recrystallizingfrom pyridine. We obtained two kinds of crystal with different colours (A and B), usingdifferent ratios of silver nitrate and α-dithionaphthoic acid (1:2,1:4) in the reactions. The structures of the two kinds of crystal were determined by a single-crystal X-raydiffraction analysis. The crystal (A) belongs to monoclinic space group C_(2h)~5-P2_1/a withunit cell parameters: a = 22.822(4) A, b = 12.803 (4) A, c = 24.444 (7) A, β = 103.90 (2)°V = 6933.14 A~3, Z = 4. The crystal (B) belongs to monoclinic space group C_(2h)~6-C2/c witha = 29.150 (2) A, b = 12.799 (3) A, c = 24.413 (2) A, β = 130.56 (4)°, V = 6914.38 A~3,Z = 4. Both crystals (A) and (B) have the same molecular configuration, but they havedifferent symmetry. In crystal (B), the molecule possesses a C_2 symmetry. This paperreports the structure determination and parameters o