SYNTHESIS AND STRUCTURE OF PERCHLORATOBIS-(2,2''''-BIPYRIDYL) COPPER (Ⅱ) PERCHLORATE

<正> C20H16Cl2CuN4O8,JMr = 574. 82,triclinic,space group PI,a =7. 397 (1),b=11. 172(3),c=15. 185(5)A,α=66. 28(2),β=76. 91(1),γ= 80. 74(2)°,V = 1115. 6A3,Z = 2,D=1. 71g·cm-3,μ=12. 76cm-1,F(000) = 582,R=0. 045,Rw = 0. 048. The Cu atom is coordinated by four N atoms from the two 2,2'-bipyridyls and two O atoms from two ClO4- groups,forming a distorted octahedron. A chain structure is developed through the coordinated ClO4-.     

SYNTHESIS AND STRUCTURE OF (Et_4N)_2[Ni_2(OSC_5H_4)_2(μ-SC_6H_4OH)_2]

<正> The synthesis and structure of cluster compound(Et4N)2[Ni2-(OSC6H4)2(u-SC6H4OH)2] are reported. Mr = 876.54,space group P21/n, a = 9.179(4), b = 17.487(6), c = 12.840(4) A;B=92.87(3)°;V=2058.6(2)A3; Z = 2; DC = 1.182g·cm-3.     

SYNTHESIS AND CRYSTAL STRUCTURE OF AZACROWN (2, 2) DINITRATE [C_(12)H_(28)O_4N_2] (NO_3)_2

<正> [C12H28O4N2](NO3)2, Mr = 388. 45, monoclinic space group P21/ n,a = 7. 811(2), b = 10.626(4), c= 11. 823(6) A , β=106.51(3)°, Z = 2, Dc = 1.37 gem-3, V = 940. 8(7) (?)3 F(000) = 416, μ(MoKα) =1. 3 cm-1, R =0. 044 for 1373 reflections. The structure contains prdtonated azacrown [H2(2,2)]2+ and two (NO3-) which are bridged by four hydrogen bonds O(nitrate) ...H-N(crown). The ion [H2(2,2)]2+ in the title crystal lies on the crystallographic center of symmetry. There is half a [H2(2,2)]2+ and one NO3- in an asymmetric unit.     

Structure and properties of dinuclear manganese(III) complexes with pentaanionic pentadentate ligands including alkoxo, amido, and phenoxo donors

Doubly bridged mu-alkoxo-mu-X (X = pyrazolato or acetato) dinuclear MnIII complexes of 2-hydroxy-N-{2-hydroxy-3-[(2-hydroxybenzoyl)amino]propyl}benzamide) (H5L1) and 2-hydroxy-N-{2-hydroxy-4-[(2-hydroxybenzoyl)amino]butyl}benzamide (H5L2), [Mn2(L)(pz)(MeOH)4].xMeOH (1, L = L1, x = 0.5; 2, L = L2, x = 0; Hpz = pyrazole) and [Mn2(L1)(OAc)(MeOH)4] (3), have been prepared, and their structure and magnetic properties have been studied. The X-ray diffraction analysis of 1 (C24.5H34Mn2N4O9.5, triclinic, P, a = 12.2050(7) A, b = 12.7360(8) A, c = 19.2780(10) A, alpha = 99.735(5) degrees , beta = 96.003(4) degrees , gamma = 101.221(5) degrees , V = 2867.6(3) A3, Z = 4), 2 (C25H34Mn2N4O9, triclinic, P, a = 9.4560(5) A, b = 11.0112(5) A, c = 13.8831(6) A, alpha = 90.821(4) degrees , beta = 92.597(4) degrees , gamma = 93.403(4) degrees , V = 1441.29(12) A3, Z = 2), and 3 (C23H32Mn2N2O11, triclinic, P, a = 10.511(5) A, b = 11.713(5) A, c = 13.135(5) A, alpha = 64.401(5) degrees , beta = 74.000(5) degrees , gamma = 66.774(5) degrees , V = 1329.3(10) A3, Z = 2) revealed that all complexes consist of dinuclear units which are further extended into 1D (1 and 3) and 2D (2) supramolecular networks via hydrogen-bonding interactions. Magnetic susceptibility data evidence antiferromagnetic interactions for all three complexes: J = -3.6 cm-1, D approximately 0 cm-1, g = 1.93 (1); J = -2.7 cm-1, D = 0.8 cm-1, g = 1.93 (2); J = -4.9 cm-1, D = 3.8 cm-1, g = 1.95 (3).     

STRUCTURE OF A Cu (Ⅱ) COMPLEX WITH MIXED LIGANDS, DIETHYLENETRIAMINE ETH YLENEDIAMINE COPPER (Ⅱ) DIPERCHLORATE

<正> CuC6H21N5O8Cl2, Mr = 425. 5, monoclinic, P21/n, a = 8. 418 (2), b = 14.450(4), c= 12. 940(3)A, β=98. 13(2)% V = 1572. 9A3,Z = 4, Dx= 1. 797g. cm-3,μ(MoKa) = 18. 3cm-1. The crystal structure consists of discrete complex cations and perchlorate anions. The coordination geometry around Cu(Ⅱ) atom is a distorted square pyramid. The complex cations are disordered in the crystal,the ethylenediamine ligand chelates to the Cu(Ⅱ ) atom in δ arid λ conformation in different cells. The average Cu-N distance is 2. 03 A in the equatorial plane while the Cu -N distance is 2. 25 A in the axial direction.     

SYNTHESIS AND CRYSTAL STRUCTURE OF (DIETHYLENETRIA-MINE) (ACETATE) ZINC PERCHLORATE

<正> The preparation and molecular structure of the novel five-coordinate zinc compound CZn(C4H13N3) (C2H3O2)]ClO4(Mr= 327. 04) are described. The crystal belongs to orthorhombic space group Pn21a with a=8. 352(2) ,6=8. 642(2) ,c=17. 758 (4)A,V=1282A3,Z=4,0c=1.69gcm-3,Dm=1.70gcm-3,F(000) = 672,u(MoKa)= 22.01cm-1.The complex cation has a distorted trigonal bipyramidal geometry wifr each acetat anion C2H3O2- bridging two zinc atoms so that a chain structure along a axis is formed by the complex cations [Zn(C4H13N3)(C2H3O2)]+.     

Chemistry of metal-bound anion radicals. A family of mono- and bis(azopyridine) chelates of bivalent ruthenium

The reaction of the dihydride [RuII(H)2(CO)(PPh3)3], 3, with excess azo-2,2'-bipyridine (abp) in boiling dry benzene has afforded the diradical bischelate [RuII(abp.-)2(CO)(PPh3)], 4, and the hydridic monochelate monoradical [RuII(abp.-)(H)(CO)(PPh3)2], 5. A similar reaction between 3 and 2-(p-chlorophenylazo)pyridine (Clpap) did not yield a bischelate, but the hydridic monoradical [RuII(Clpap.-)(H)(CO)(PPh3)2], 6, has been isolated. Upon treatment of 4-6 with NH4PF6 in a wet dichloromethane-acetonitrile medium, the one-electron-oxidized salts 4+PF6-, 5+PF6-, and 6+PF6- are isolated, H+ being the oxidizing agent. The X-ray structures of 4+PF6-.CH2Cl2, 5+PF6-.H2O, and 6+PF6- have been determined. In the monoradical 4+ the azo N-N bond lengths in the two chelate rings are 1.284(6) and 1.336(6) A, showing that the radical electron is localized in the latter ring. The half-filled extended Hückel HOMO is indeed found to be so localized, and it has a large azo character. Complexes 4-6 display radical redox couples with E1/2 in the range -0.5 to +0.10 V vs SCE. The E1/2 values qualitatively correlate with corresponding vco values (1900-2000 cm-1). The monoradicals (S = 1/2) 4+, 5, and 6 uniformly display a strong EPR signal near g = 2.00. Metal-mediated magnetic interaction makes the EPR-silent diradical 4 strongly antiferromagnetic with J = -299 cm-1. Crystal data are as follows: (4+PF6-.CH2Cl2, C40H33Cl2F6N8-OP2Ru) monoclinic, space group P2(1)/c (no. 14), a = 14.174(6) A, b = 16.451(4) A, c = 18.381(4) A, beta = 98.00(3) degrees, Z = 4; (5+PF6-.H2O, C47H41F6N4O2P3Ru) monoclinic, space group P2(1)/n (no. 14), a = 9.433(2) A, b = 38.914(17) A, c = 13.084(3) A, beta = 103.47(2) degrees, Z = 4; (6+PF6-, C48H39ClF6N3OP3Ru) monoclinic, space group P2(1)/n (no. 14), a = 10.496(5) A, b = 22.389(8) A, c = 19.720(6) A, beta = 90.53(3) degrees, Z = 4.     

H_(3+n)[AsMo_(12-n)V_nO_(40)]·9H_2O(n=2—4)的结构

X光晶体结构分析证实H_(3+n)[AsMo_(12-n)V_+nO_(40)]·9H_2)(n=2—4)的晶体同构,空间群为P,Z=2。n=2时,a=13.951(5),b=14.137(5),c=13.556(4),α=112.44(2),β=109.49(3),γ=60.77(3)°,V=2120.2,M_r=1943.36,D_c=3.044g.cm~(-3),μ=40.90cm~(-1),F(000)=1828。用6216个I>3σ(I)的独立衍射精修结构,R=0.082;n=3时,a=13.891(7),b=14.076(5),c=13.483(5)A,α=112.34(3),α=109.26(3),γ=60.82(3)°,V=2094.5,M_r=1899.37,D_c=3.011g.cm~(-3),μ=40.63cm~(-1),F(000)=1792。用6699个I>3σ(I)的独立衍射精修结构,R=0.054;n=4时,a=13.854(3),b=14.099(2),c=13.501(4),α=112.09(2),β=109.13(2),γ=61.03(2)°,V=2103.0,M_r=1855.38,D_c=2.92(悬浮法),D_c=2.930g.cm~(-3),μ=39.71cm~(-1),F(000)=1756。用7613个I>3σ(I)的独立衍射精修结构,R=0.044。实验采用MoKα辐射,λ=0.71073,T=296K。杂多阴离子均呈准Keggin结构,12个金属原子呈无序分布,可以M(Mo/V)表示。AsO_4四面体中As—O键长1.66—1.68,O—As—O键角均在109.5°左右。畸变的MO_6八面体中,M—O键长分布在1.63—2.36范围。水分子无序处在晶胞中十四个位置上,除O_w(12)和O_w(13)外的水分子均与杂多阴离子形成氢键,且水分子间形成如沸石中那样的复杂?     

METAL COMPLEXES OF POLYCYCLIC TERTIARY. AMINES. PART VIII. SYNTHESIS AND CRYSTAL STRUCTURE OF 1,4-DIAZABICYCLO[2.2.2]OCTANEPENTACARBONYLMOLYBDENUM(0), (CH_2)_6N_2·Mo(CO)_5

<正> C11H12N2MoO5, Mr = 348.17, orthorhombic, space group p212121,a= 7.048(1), b = 11.060(4), c = 18.039(7) A, V = 1406.2(8) A3, Z = 4, D x=1.645, Dm = 1.61 (flotation in aqueous KI) g cm-3 , graphite-monochromatizedMo-Kα,λ = 0.71069 A, μ = 9.25 cm-1, F(OOO) = 695.73, T = 295°K, final RF =0.035 and RwF2 = 0.051 for 1335 observed reflections with |F0| > 3σ(|F0|). The measured molecular dimensions.reflect the trans influence and steric bulk of the organic cage ligand.     

MOLECULAR STRUCTURE AND SPECTRAL STUDIES OF Ni(ENAC)

<正> C12H20N2O2Ni,Mr = 283. 02, orthorhombic, Pbn21 ,a = 10. 269 (2), b = 12. 182(2),c= 10. 348(1) A,V=1294.5 A3,Z = 4,DC = 1. 452 g/cm3,MoKa radia-tion(λ= 0.71073 A ) ,μ= 14. 96 cm-1, F (000) = 600, R = 0. 058 for 1131 reflections. The Ni (Ⅱ ) ion in This molecule has a square planar configuration. The three chelate rings formed by Ni atom and ENAC2- are coplanar with the plane of NiO2N2. Ultra violet-visible and IR spectra are in agreement with the crystal structure data.     

STRUCTURE OF N-(p-CHLORO )-PHENYL ZMINODIACETIC ACID

<正> N-(para-chloro)-phenyl iminodiacetic acid hydrate ethanol solvate ClC6H4N(CH2COOH)2· H2O·C2H5OH, Mr = 307.73, monoclinic, P21/n, Cu-Ka (λ=1. 5410(?)), a = 16. 732(1), b = 5. 337(1), c=16. 300(1)(?) ,β=108. 52(1)°, V = 1380. 1(?)3, Z = 4, Dc=1.481g.cm-3, * = 27. 172cm-1, F(000) = 648, final R = 0. 072 for 1610 observed reflections. The crystal structure consists of discrete molecule of N-(para-chloro)-phenyl iminodiacetic acid, hydrate as well as ethanol solvate. A big ring consisting of atoms O(3), C(3), C(4), N(1), C(2), C(1), O(2) and H(2) is nearly planar with the maximum deviation of the atom N(1) of 0. 54 (?). Owing to the intramolecular hydrogen bond O(2)-H(2)…O(3) , the bond C(3) -O(3) in the COOH group is longer than the bond C(3)-O(4).     

CRYSTAL STRUCTURE OF ORGANOMETALLIC COMPLEX [Zn（pom）2Br2]

<正> Organometallic complex [Zn (pom)2Br2] (pom = 3-M ethyl-4-Ni-tropyridine-1-Oxide), C12H12Br2N4O6Zn, MT = 533. 44, triclinic, P1, a = 11. 450 (3), b = 13. 027(2), c=6. 605(1)A, α=101. 25(1),β=96. 96(2), γ=108. 06 (2)°,V = 901.2(4)A3, Z = 2, Dc=1. 97 gcm-3,λ(MoKa) = 0. 71069A , F(OOO) = 520, μ= 58. 21cm-1, final R = 0. 040 for 2192 observed reflections, T = 296K. The compound is a mononuclear complex, containing a tetrahedrally coordinated zinc atom.     

两种单齿硫醇为配位体的钼络合物的合成和结构表征

本文报导利用MoC1_5、NaOMe、C_6H_5CH_2SH和NaHS在无氧、无水,室温条件下在甲醇介质中合成(Et_4N)_2[Mo_2O_2S_2(SCH_2C_6H_5)_4](化合物Ⅰ)和(Et_4N)-[Mo_2O_2(μ-SCH_2C_6H_5)_3(SCH_2C_6H_5)_4](化合物Ⅱ)的反应条件,分离步骤。本文同时报导这两种化合物的核磁共振谱、红外光谱、电子光谱等结构表征,同时也对化合物形成的可能机理作了探索性的讨论。     

CRYSTAL STRUCTURE OF [Ni((C)_6H_(11)O)_2PS_2)·(C_4H_9NH_2)_4]-(C_6H_(11)O)_2PS_2

<正> [Ni((C6H11O)2PS2)·(C4H9NH2)4](C6H11O)2PS2,Mr-=938. 05, triclinic,P1,a=13. 513(6),b=16. 040 (7), c= 12. 891(6) A , α= 95. 66 (4),β= 90. 23(4),γ= 75. 46(3)°,V = 2691 A3,Z=2,Dc= 1. 16 g·cm3.μ=6. 07cm-1,MoKa radiation, λ=0. 71069 A ,F(000) = 1020,R=0. 100 for 4595 reflections with I≥3σ(I). The title compound molecule consists of a complex cation [Ni((C6H11O)2PS2)(C4H9-NH2)4]+ and a complex anion (C6H11O)2PS2- . The Ni (Ⅱ) atom in the cation is octahedrally coordinated by four nitrogen atoms from four w-butylamine ligands and two sulfur atoms from one (C6H11O)2PS2 group.     

CRYSTAL STRUCTURE OF {Ni[(C_4H_9O)_2PS_2](C_(12)H_8N_2)_2} -[(C_4H_9O)_2PS_2]

<正> {Ni C(C4H9O)2PS2] (C12H8N2)2} [C(C4H9O)2PS2], Mr= 795. 60, Monocinic,P2,/n,a=16. 806(2), b=12. 720(2), c=21. 248(2) A. β=98. 454(7)°, V = 4493A3,Z=4,Dc= 1. 18g·cm-3,Mo Ka radiation,A=0. 71069A ,F(000) = 1664, R=0. 102 for 4154 reflections with I≥3σ(I).The crystal structure consists of complex cation {NiC(C4H9O)2PS2](C12H8N2)2}+ and complex anion C(C4H9O)2PS2]-. In the cation, nickel (Ⅱ) atom is coordinated by four nitrogen atoms and two sulfur atoms to form a distorted octahedron.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE HEXANUCLE-AR DIAZENIDO-OXOMOLYBDATE [(n-C_4H_9)_4N]_3[Mo_6O_(18)-(N_2C_6H_3-2,4-(NO_2)_2]

<正> Crystal of the title complex [(n-C4H9)4N]3[Mo6O18(N2C6H3-2,4-(NO2)2](Mr= 1710. 5) is orthorhombic with space group P21cn (Pna21), a = 17. 304(3), b = 17.580(2), c=24. 355(4) (?), V = 7409(2)(?)3, Z = 4, Dc=1. 60g/ cm3, μ=10. 29cm-1, F (000) = 3647. The structural solutions and refinements based on 3900 reflections (I≥3σ(I)) converged at R = 0. 0575, Rw =0. 0498. The atoms of Mo(3), Mo(4), O(1), O(5), O(9), O(11) and the [N2C6H3-2,4-(NO2)2] unit in the complex anion locate approximately in a plane about which the complex anion is nearly symmetrical.     

STUDIES ON THE MOLECULAR STRUCTURE OF WT-12 DERIVATIVE OF PYRAZOLO [3,4-d] - 1,3,2-DIAZAPHOSPHORIN-6-ONE

<正> The title compound was obtained by reaction of 1-phenyl-5-benzy-lamino-pyrazole-4-(N-methyl) carboxamide with p-fluorophenyl phosphorus dichloride and its molecular structure determined by X-ray diffraction method. The crystal is mono-clinic,space group P21/c,with a=11. 874(2),b= 12. 986(2),c=14. 587(2) A ,β= 106. 21(1)°,V=2159. 6A3,Mr = 430. 43(C24H20N4OFP),Z=4, Dx = 1. 324g/cm-3,μ(MoKa) = 1. 53cm-1 ,and F(000) = 896. The atoms in the pyrazolo[3,4-d] - 1,3,2-di-azaphosphorin-6-one are coplanar except the P atom.     

Three new polynuclear copper(II) complexes with the symmetric [Cu(mu1,1-N3)2Cu]2+ core and pyridine derivatives: syntheses,structure, and magnetic behavior

Three new polynuclear copper(II) complexes, derived from the end-on azido bridging ligand and pyridine derivatives, have been synthesized, and their crystal structures have been determined by X-ray diffraction methods; they are the dinuclear compounds [Cu2(mu 1,1-N3)2(4-Etpy)4(mu-NO3)2] (1), and [Cu2(mu 1,1-N3)2(3-ampy)4(mu-NO3)2]. C2H5OH (2), and the trinuclear [Cu3(mu 1,1-N3)4(N3)2(Meinic)2(DMF)2] (3). 4-Etpy is 4-ethylpyridine, 3-ampy is 3-aminopyridine, and Meinic is methylisonicotinate. Compound 1, C28H36Cu2N12O6, crystallized in the monoclinic system, space group P2(1)/n, with a = 12.355(9) A, b = 12.474(4) A, c = 12.854(6) A, beta = 117.68(4) degrees, and Z = 2. Compound 2, C22H30Cu2N16O7, crystallized in the triclinic system, space group P1, with a = 9.695(2) A, b = 10.895(2) A, c = 7.909(2) A, alpha = 96.81(3) degrees, beta = 96.40(3) degrees, gamma = 96.56(3) degrees and Z = 1. Compound 3, C20H28-Cu3N22O6, crystallized in the monoclinic system, space group P2(1)/n, with a = 7.755(2) A, b = 14.680(5) A, c = 15.810(5) A, beta = 102.81(2) degrees, and Z = 2. 1-3 have the symmetric [Cu(mu 1,1-N3)2Cu]2+ core and structural parameters outside the previously reported range. Magnetic susceptibility data, measured from 2 to 300 K, show strong ferromagnetic coupling for the dinuclear end-on compounds 1 and 2 and bulk moderate ferromagnetic coupling for the trinuclear compound 3. These data were fitted to the appropriate equations derived from the Hamiltonian H = -JS1S2 for 1 and 2 and from the Hamiltonian H = -J1(SA1SB + SA2SB) - J2SA1.SA2 for 3, giving the parameters J = 230.1(1) cm-1, g = 2.17(0.01) for 1, J = 223.2(2) cm-1, g = 2.16(0.01) for 2, and J1 = 47.3(2) cm-1, J2 = -22.5(1) cm-1, gA = 2.26(0.02), gB = 2.07(0.03) for 3. The magnetic susceptibility data can be correlated with the structural parameters.     

Vanadium complexes of the N(CH2CH2S)3(3-) and O(CH2CH2S)2(2-) ligands with coligands relevant to nitrogen fixation processes

Vanadium(III) and vanadium(V) complexes derived from the tris(2-thiolatoethyl)amine ligand [(NS3)3-] and the bis(2-thiolatoethyl)ether ligand [(OS2)2-] have been synthesized with the aim of investigating the potential of these vanadium sites to bind dinitrogen and activate its reduction. Evidence is presented for the transient existence of (V(NS3)(N2)V(NS3), and a series of mononuclear complexes containing hydrazine, hydrazide, imide, ammine, organic cyanide, and isocyanide ligands has been prepared and the chemistry of these complexes investigated. [V(NS3)O] (1) reacts with an excess of N2H4 to give, probably via the intermediates (V(NS3)(NNH2) (2a) and (V(NS3)(N2)V(NS3) (3), the V(III) adduct [V(NS3)(N2H4)] (4). If 1 is treated with 0.5 mol of N2H4, 0.5 mol of N2 is evolved and green, insoluble [(V(NS3))n] (5) results. Compound 4 is converted by disproportionation to [V(NS3)(NH3)] (6), but 4 does not act as a catalyst for disproportionation of N2H4 nor does it act as a catalyst for its reduction by Zn/HOC6H3Pri2-2,6. Compound 1 reacts with NR1(2)NR2(2) (R1 = H or SiMe3; R2(2) = Me2, MePh, or HPh) to give the hydrazide complexes [V(NS3)(NNR2(2)] (R2(2) = Me2, 2b; R2(2) = MePh, 2c; R2(2) = HPh, 2d), which are not protonated by anhydrous HBr nor are they reduced by Zn/HOC6H3Pri2-2,6. Compound 2b can also be prepared by reaction of [V(NNMe2)(dipp)3] (dipp = OC6H3Pri2-2,6) with NS3H3. N2H4 is displaced quantitatively from 4 by anions to give the salts [NR3(4)][V(NS3)X] (X = Cl, R3 = Et, 7a; X = Cl, R3 = Ph, 7b; X = Br, R3 = Et, 7c; X = N3, R3 = Bu(n), 7d; X = N3, R3 = Et, 7e; X = CN, R3 = Et, 7f). Compound 6 loses NH3 thermally to give 5, which can also be prepared from [VCl3(THF)3] and NS3H3/LiBun. Displacement of NH3 from 6 by ligands L gives the adducts [V(NS3)(L)] (L = MeCN, nu CN 2264 cm-1, 8a; L = ButNC, nu NC 2173 cm-1, 8b; L = C6H11NC, nu NC 2173 cm-1, 8c). Reaction of 4 with N3SiMe3 gives [V(NS3)(NSiMe3)] (9), which is converted to [V(NS3)(NH)] (10) by hydrolysis and to [V(NS3)(NCPh3)] (11) by reaction with ClCPh3. Compound 10 is converted into 1 by [NMe4]OH and to [V(NS3)NLi(THF)2] (12) by LiNPri in THF. A further range of imido complexes [V(NS3)(NR4)] (R4 = C6H4Y-4 where Y = H (13a), OMe (13b), Me (13c), Cl (13d), Br (13e), NO2 (13f); R4 = C6H4Y-3, where Y = OMe (13g); Cl (13h); R4 = C6H3Y2-3,4, where Y = Me (13i); Cl (13j); R4 = C6H11 (13k)) has been prepared by reaction of 1 with R4NCO. The precursor complex [V(OS2)O(dipp)] (14) [OS2(2-) = O(CH2CH2S)2(2-)] has been prepared from [VO(OPri)3], Hdipp, and OS2H2. It reacts with NH2NMe2 to give [V(OS2)(NNMe2)(dipp)] (15) and with N3SiMe3 to give [V(OS2)(NSiMe3)(dipp)] (16). A second oxide precursor, formulated as [V(OS2)1.5O] (17), has also been obtained, and it reacts with SiMe3NHNMe2 to give [V(OS2)(NNMe2)(OSiMe3)] (18). The X-ray crystal structures of the complexes 2b, 2c, 4, 6, 7a, 8a, 9, 10, 13d, 14, 15, 16, and 18 have been determined, and the 51V NMR and other spectroscopic parameters of the complexes are discussed in terms of electronic effects.     

CRYSTAL STRUCTURES OF TWO DITHIOLATO-COPPER COMPLEXES (Ph_4P)Cu(BDT)_2 AND (Ph_4P)Cu(TDT)_2

<正> [(C6H5)4P]Cu(S2C6H4)2(Ⅰ),Mr = 683. 39,monoclinic,space group C2/c,a=16. 099 (4),b= 11. 913(3) ,c = 16: 715(9) A ,β=97. 13(4)°, v = 3180. 7 A3,z=4.MoKa radiation,λ= 0. 71069A ,Dc= 1. 427g/cm3,μ= 10. 1cm-1,F(000) = 1400,R=0. 061 and Rw = 0. 068 for 2189 reflections with Ⅰ>3σ(Ⅰ). [(C6H5)4P]Cu (S2C7H6)2(Ⅰ),Mr = 711. 45,monoclinic,space group C2/c,a=16. 501(6),b = 37. 461 (15),c=16. 684(4)A,β=96. 70(4)°, v= 10248. 8(46) A3,z= 12. MoKa radiation, λ= 0. 71069A,Dc=1.383g/cm3,μ=9. 45cm-1,F(000).= 4416,R= 0. 074 and Rw= 0. 078 for 2085 reflections with I>2σ(I)(1). The copper atom in the complexes is surrounded by four sulfur atoms from two dithiolato ligands in an approximate, square-plane. The average Cu-S distances of the copmplexes(Ⅰ) and (Ⅱ) are 2. 179 and 2. 178 A, respectively.