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.     

CRYSTAL STRUCTURES OF ISOMERS OF DIHYDROXYDIBENZO—14—CROWN—4

<正> C18H18O6·H2O, Mr = 348. 34, cis-isomer: orthorhombic, Cmc21, a = 16. 421(3), 6 = 11.978(1), c=8. 624(1)(?), V = 1696. 2(?)3, Z = 4, Dc= 1.293 gcm-3, λ(MoKα) = 0. 71073(?), μ = 0. 911cm-1, F (000) = 763, R = 0. 043, Rw = 0. 042 for 769 unique observed reflections. trans-Isomer : orthorhombic, Cmc21, a = 16. 503(2), b = 12. 297(2), c=8. 557(3) (?). V = 1736(?)3, Z = 4, Dc= 1.271 gem-3, λ(MoKα) = 0. 71073(?), μ = 0. 892cm-1, F (000) = 736, R=0.048, Rw = 0. 046 for 551 unique observed reflections. The configurations of the two molecules appear as butterflies. There is a Cm symmetry in the molecule of each isomer.     

SYNTHESIS AND CRYSTAL STRUCTURE OF MoS4Cu4I2（Py）6

<正> C30H30Cu4I2S4MoN6,Mr=1206, orthorhombic, Fdd2, a = 22. 511(4), b= 22.946(4), c=30. 742(6)(?), Z = 16, Dc = 2. 019g/cm3, V = 15879.4 (?)3, μ = 41. 884cm-1, F (000) = 9280. The final R factor is 0. 0279 for 1884 observed reflections with I>3σ(I). Crystal structure analysis shows that the MoS4Cu4 aggregate is formed, each the four copper atoms is linked with two S atoms of the te-trahedral MoS42- core. The average distance between Mo and Cu atoms is 2. 678(?).     

CRYSYTAL AND MOLECULAR STRUCTURES OF η~8-CYCLOOC-TATETRAENYLLANTHANIDE COMPLEXES [(η~8-C_8H_8)LnCl-(OC_4H_8)_2]_2(Ln=Pr, Nd)

<正> Complexes [(η8-C8H8)LnCl(OC4H8)2]2, (Ln = Pr(1), Nd(2)) both crystallize in monoclinic space group P21/n with cell dimensions for 1: a = 11. 860(3), b=12. 697(3), c=12. 161(2)(?), β=111. 88(2)°, V= 1699. 50(69) (?)3, Dc=1. 66gcm-3,Z==2 (4 monomers), μc=30. 2cm-1, F (000) = 848, the final R = 0. 031, Rw = 0. 032 for 2303 independent reflections with I≥ 3σ(I) ; and for 2: a=11. 834(4), b = 12. 666(5), c=12. 166(3)(?), β=111. 73(2)°, V= 1694. 03 (99)(?)3, Dc= 1. 68g. cm-3, Z = 2 (4 monomers), μc=32. 3cm-1, F(000) = 852, R=Rw = 0. 035 for 3487 independent reflections with I≥3σ(I). In each complex, there are two Ln atoms in a dimeric unit which are bridged asymmetrically by two chloride ions with Ln - Cl bond lengths of 2. 847(2) and 2. 924(2)(?) for 1, or 2. 836(1) and 2. 919(2)(?) for 2. The cyclooctatetraene COT dianion ring is planar with eightfold molecular symmetry and an average C -C bond length of 1. 392(?). It is symmetrically coordinated to the Ln atom with an average Ln - C distance of     

STRUCTURAL STUDY ON HETEROCYCLIC CARBENE-CONTAIN-ING IRON CARBONYL CLUSTER-STRUCTURES OF Fe_3(CO)_8-[CNH C(CH)_4CNH](μ_3-S)_2

<正> The title cluster Fe3(CO)8[CNH C(CH)4CNH] (μ3-S)2 has beensynthesized and its crystal and molecular structure determined. Crystal data: C15 H6N2O8S2Fe3, Mr = 646. 27, triclinic, space group P1, a = 8. 6664(1), 6=10. 7857 (2), c=12.5536(3)(?),α=112. 3944(2), β=106. 4103(2) ,γ = 95.541(1)°, V = 1012. 8(?)3. Z = 2, Dc=1. 888gcm-3, μ=23. 639cm-1, final R = 0. 0477, Rw =0. 0535 for 2583 independent reflections. The cluster is a carbene derivative of Fe3-(CO)9S2, and contains a heterocyclic fragment c as the carbene ligand whichreplaces a terminal axial CO ligand of atom Fe(l) and locates in a vertical position to the distorted basal plane formed by Fe(1)S(1)Fe(2)S(2). The geometry of Fe3-(CO)9(μ3-S)2 has been maintained in the title compound but some of the Fe-S bond lengths have been changed.     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound [Et4N ] 2 [Mo2 (CO) 8 (SC6H4-OCH3-p) 2]

Reaction of Mo(CO)6 with p-H3CO-C6H4SNa and Et4NCl · H2O in CH3CN afforded a dinuclear molybdenum(0) compound [Et4N]2[Mo2 (CO)8 (SC6H4-OCH3-p)2] (1). The crystal structure was determined by X-ray diffraction. The crystallographic data: C38H54Mo2N2O10S2, Mr = 954.87, triclinic, P-1, a = 11.348 (7), b =11.616(5), c=10.065(7) A, a=113.86(4), β=111.39(5), γ=91.92(5)°, V=1104.0(1) A3, Z=1, Dc=1.44 g/cm3, F(000)=492, μ=7.0cm-1, Final R=0. 046 and Rw=0. 049 for 2657 reflections with I＞3. Oσ(I). The X-ray structure analysis revealed that the Mo2S2 core of 1 is planar. The geometry around each Mo atom is a distorted octahedron, the two octahedrons form an edge-sharing bioctahedron. The bond. In addition, the 95Mo NMR chemical shift of 1 is discussed.     

Synthesis and Structure of a Dimolybdenum Carbonyl Compound with Thiolato-Bridges [Et4N] 2 [Mo2 (CO) 8 (SC6H4-Cl -p) 2]

Reaction of Mo (CO)6 with p-Cl-C6H4SNa and Et4NCl · H2O in CH3CN afforded a dinuclear molybdenum (0) compound [Et4N]2 [Mo2 (CO)8 (SC6H4-Cl-p)2] (1). The crystal structure was determined by X-ray diffraction. The crystallographic data: C36H48Cl2Mo2N2O8S2, Mr= 963.71, monoclinie, P21/c, a=9. 269(4),b=13.750(3), c=17.466(6) A ;β=104.84(3)°; V=2151.8(3) A3; Z=2; Dc=1.49 g/cm3; F(000)=984; μ=8.3 cm-1; MoKα radiation (λ=0. 71073A ); Final R = 0. 055 and Rw=0. 065 for 3287 reflections with I＞3. 0σ(I). The X-ray structure analysis revealed that the Mo2S2 core is planar. The geometry around each Mo atom is a distance is 4. 014(2) A , and this obviously indicates the absence of Mo-Mo bond.     

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)(?).     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound[Et4N]2[Mo2(CO)8(SC6H4-CH3-p)2]

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｉｎｃｅｔｈｉｏｌａｔｅｌｉｇａｎｄｗａｓｉｎｔｒｏｄｕｃｅｄｉｎｔｏｍｏｌｙｂｄｅｎｕｍｃａｒｂｏｎｙｌｃｏｍｐｏｕｎｄｉｎ1 984 [1],ｔｈｅｉｎｖｅｓｔｉｇａｔｉｏｎｏｎｌｏｗ ｖａｌｅｎｃｅＭｏ -ＳＲｃｏｍｐｏｕｎｄｓｈａｓｒｅｃｅｉｖｅｄａｔｔｅｎｔｉｏｎｆｏｒｔｈｉｓｋｉｎｄｏｆｌｏｗ ｖａｌｅｎｃｅｃｏｍｐｏｕｎｄｓｐｏｓｓｅｓｓｃｅｒｔａｉｎａｄｖａｎｔａｇｅｏｎｃｏｍｐｏｕｎｄｓｙｎ ｔｈｅｓｉｓ,ｍｏｌｅｃｕｌｅｓｔｒｕｃｔｕｒｅａｎｄｐｈｙｓｉｃａｌａ…     

反式和顺式含磷稠环6,13-二硫丙基-5,12-二氧-6,13-二硫羰基-6a,7,13a,14-四氮-6,13-二磷杂二苯并(a,h)蒽烷的晶体结构

采用X射线分析测定了标题化合物的晶体结构和分子结构。化合物C_(20)H_(22)-O_2N_4P_2S4(1)为反式构型,M_r=540.63,正交晶系,空间群Pcab,a=7.255(2),b=18.297(3),c=18.576(2),V=2465.9 ~3,Z=4,D_c=1.456g/cm~(-3),最终偏离因子R=0.058,R_ω=0.049;化合物(2)为顺式构型,单斜晶系,空间群Ic,a=14.649(5),b=7.009(2),c=22.694(8),β=100.60(3)°,V=2290.1 ~3,Z=4,D_c=1.643g/cm~(-3),最终偏离因子R=0.061,R_ω=0.065。晶体结构测定结果表明,这对顺反异构体的构象明显不同:反式异构体的分子本身有对称中心且与晶体学对称中心重合,氧,氮,磷杂六员环为椅式构象,磷硫单键为轴向键,磷硫双键为平伏键;顺式异构体的分子本身无对称中心,两个氧氮磷杂六员环分别为椅式和船式构象,环上的磷硫单键为平伏键,磷硫双键为轴向键,与反式异构体恰恰相反。     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound〔Et_4N〕_2〔Mo_2(CO)_8(SC_6H_4-NH_2-p)_2〕

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｅｘｉｓｔｅｎｃｅａｎｄｓｉｇｎｉｆｉｃａｎｃｅｏｆｔｈｅｍｏｌｙｂｄｅｎｕｍ ｓｕｌｆｕｒｂｏｎｄｉｎｇｉｎｍｏｌｙｂｄｅｎｕｍｅｎｚｙｍｅｓ〔１〕ｈａｖｅｓｔｉｍｕｌａｔｅｄｔｈｅｓｔｕｄｉｅｓｏｎｔｈｅｃｈｅｍｉ...     

Synthesis and Structure of a New Dinuclear Molybdenum(I) Compound with Cyclohexanthiolate Ligand, [Mo_2(SC_6H_(11))_2(CO)_6(CH_3CN)_2]

1 INTRODUCTION The chemistry of complexes containing low-valence molybdenum and tungsten metal atoms hasincreasingly attracted the attention from chemistsand bioinorganic chemists due to their significancefor studying metal enzymes[1～5]. Since the s…     

CRYSTAL AND MOLECULAR STRUCTURE OF A PENTA-COOR-DINATED SILVER COMPLEX, SILVER 8-HYDROXYQUINOLINE-5-SULFONATE AgC_9H_8NO_4S

<正> AgC9H6NO4S, Mr = 332. 1, monoclinic, space group P21/c, a = 8. 292(1), b = 10. 394(2), c=10. 852(2)A, β=102. 73(1)°, V =912. 4(?)3, Z = 4, Dc = 2. 417gcm-3, λ(MoKα) = 0. 71073(?) , μ = 24. 0cm-1, F (000) = 648, final R =0. 041, Rw = 0. 047 for 1369 observed reflections. The coordination polyhedron of Ag(I) is penta-coordinated square pyramid.     

STUDIES OF RARE EARTH METAL COMPLEXES OF AMINO ACIDS AND PEPTIDES. SYNTHESES AND CRYSTAL STRUCTURES OF TRIAQUO TRIS (N-ACETYLGLYCINE) LANTHANIDE Ln(CH_3CONHCH_2COO)_3(H_2O)_3(Ln = Nd~(3+),Eu~(3+) and Er~(3+))

<正> The title complexes were synthesized and their crystal structures were determined. These complexes crystallize in trigonal space group R3 with 3 molecules in a unit cell and are isostructural to each other. Crystallographic data: complex 1, Nd(CH3CONHCH2COO)3(H2O)3, Mr = 546. 6, a= 16. 582(4), c = 5. 982(2)(?), V= 1424. 5(8)(?)3, Dc=1. 91gcm-3, F (000) = 819, μ = 28.06cm-1, R(Rw) = 0. 048(0. 061); complex 2, Eu (CH3CONHCH2COO)3 (H2O)3, Mr = 554.3, a = 16.564(10), c=5.974(3)(?), V = 1418(2)(?)3,Dc= 1. 95gcm-3, R (Rw) = 0. 018 (0. 025), F (000) = 828, μ= 33. 83cm-1; complex 3, Er-(CH3CONHCH2COO)3(H2O)3, Mr = 569. 6, a = 16. 476(7), c=5. 946(6)(?), V = 1398(2) (?)3, D, = 2. 03gcm-3, R (Rw ) = 0. 020 (0. 027) , F (000) = 843, μ= 46. 25cm-1. These complexes adopt mononuclear structure, in which Ln(Ⅲ) ion is coordinated to six oxygen atoms from three ligands and three oxygen atoms from water molecules with the polyhedron of 4,4,4-tricapped triangular prism. The carboxy-lato group of the ligand bonds to Ln     

Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

CRYSTAL STRUCTURE OF [（bpy）2Ru（4,5—DIAZAFLUOREN—9—ONE][PF6]2

<正> V31H22F12N6OP2Ru, Mr = 885.6. Monoclinic, space group P21/n, a=9. 444(4), b = 14.050(7), c=25. 88(1)(?), β=92. 64(4)°, V = 3429.79(?)3, Dc=1. 712gcm-3, F(000) = 1760, μ= 6. 376cm-1, Z = 4, R=0. 077, Rw = 0. 090. There are three different Ru -N bonds of 2. 03(?), 2. 08(?) and 2. 13(?), respectively, to the two bpy and diazafluoren-9-one ligands in the complex.     

OXIDATION DECARBONYLATION OF NH_4[Mo(CO)_5I]: SYNTHE-SES AND CRYSTAL STRUCTURES OF CMo(S_2CNC_4H_8)_4]I_3 · C_7H_8 and Mo_2S_2O_2(S_2CNC4H_8)_2

<正> Both of the title complexes were produced by oxidative decarbony-lation of NH4 CMO (CO)5I]. The complexes CMo(S2CNC4H8)4]I3 ?C7H8(1) and Mo2S2O2 (S2CNC4H8)2(2) both crystallize in triclinic, space group P1 with cell dimensions for (1) : a=13. 554(4), b=13. 620(4), c= 13. 058 (4) A , α=95. 58 (3), β=105. 38(2), γ=115. 49(2)°,V = 2035(1) A3, Z=2, Dc=1. 89 g. cm-3, final R=0. 054 and Rw = 0. 062 for 2926 observed reflections; and for (2): a = 8.730(2), b=16.592(6), c = 6. 688(2)A, α=97. 67(3), β=98. 10(2), γ=80. 26(2)% V = 939. 2(5) A3, Z = 2, Dc = 2. 05 g. cm-3, final R = 0. 038 and Rw = 0. 046 for 2248 observed reflections. The Mo(V) atom is bonded to eight S atoms in distorted dodecahedron for (1). The Mo atoms in compound (2) are bridged by two S atoms and each Mo atom is coordinated by two S atoms from S2CNC4H8 and one O atom to form distorted tetragonal pyramid.     

Crystal Structure of [CH_3CH(OH)COO]_2Fe(H_2O)_2·H_2O

<正> The title compound C6H16O9Fe, Mr = 288. 13, was synthesized and crystallized in monoclinic space group P21/c, a = 9. 409(4), b = 5. 812(4), c= 22. 122(7)(?) , β=90. 80(3)°. V = 1209. 6(?)3, Z = 4, Dc=1. 572g/cm3, F(000) = 592, μ = 12. 73cm-1, R = 0. 063, Rw= 0. 068 for 1191 observed reflections. The iron atom is surrounded by O(1 - 6) in a distorted octahedron.     

APPLICATION OF DITHIO - MOLYBDATE IN THE SYNTHESES OF Mo-Cu CLUSTERS: SYNTHESES AND CRYSTAL STRUC-TURES OF MoOS_3(CuPPh_3)(Cu(PPh_3)_2 AND (Ph_4P)_2[Mo_2Cu_5S_6O_2-(S_2CNEt_2)_3] ·DMF

<正> The reactions of (NH4)2MoO2S2 with Cu(PPh3)3Cl in CH3CN in the air, or with CuCl, Ph4PBr, and NaS2CNEt2 in DMF under anaerobic condition, afforded the cluster complexes MoS3OCu2 (PPh3)3 (Ⅰ) and (Ph4P)2 CMo2Cu5S6O2-(S2CNEt2)33 · DMF (Ⅱ), respectively. Compound (Ⅰ), MoOS3Cu2P3C54H45(Mr = 1121. 0) , crystallizes in the triclinic, space group P1 with cell parameters a = 14. 103 (3), b = 17.906(3), c=11.503(2)(?), α=107. 76(1), β=111.81(2), γ = 74.93 (2)°, F = 2532. 9(?)3 and Z=2, Dc=1. 471 g/cm3, F (000) = 1140, μ(MoKα) = 13. 215 cm-1, final R = 0. 060 (Rw = 0.064) for 5959 independent reflections with I >3σ(Ⅰ). Complex (IⅡ), Mo2O3S12Cu5P2N4C66H77 (Mr = 1930. 67) , crystallizes in monoclinic, space group P2/c with cell parameters a = 25. 325(19) , 6 = 22. 506(9) , c =14. 066(8)(?) , β =100. 96(6)°, V =7871. 16 (?)3, Z = 4, D,= 1. 629 g/cm3, F(000) = 3904, μ(MoKα) = 20. 216 cm-1, R = 0. 097 (Rw = 0. 095) for 5677 reflections with I>3σ(Ⅰ). The core structure of complex (Ⅰ) is defective cub     

Synthesis and Structure of a New Dinuclear Molybdenum(Ⅰ) Compound with Cyclohexanthiolate Ligand, [Mo2(SC6H11)2(CO)6(CH3CN)2]

The reaction of [Et4N]2[Mo2(SC6H11)2(CO)8] and I2 in MeCN affords a new dinu- clear molybdenum(Ⅰ) complex [Mo2(SC6H11)2(CO)6(CH3CN)2] 1 (Mr = 672.46). The crystal and molecular structures have been determined by X-ray single-crystal diffraction. 1 crystallizes in monoclinic, space group P21/c with a = 9.302(1), b = 15.514(2), c = 9.307(1)(°A), β = 92.979(2)o, V = 1341.4(3)(°A)3, Z = 2, Dc = 1.665 g/cm3, μ = 11.28 cm-1, F(000) = 676, R = 0.0461 and wR = 0.1274 for 1702 observed reflections with I > 2σ(I). 1 possesses a rhombic bimetallic core MoS2Mo with the Mo-Mo bond length of 2.9712(4)(°A) and Mo-S of 2.4821(5)(°A).