STRUCTURE OF（C6H5COCHCOC6H5）SmI2（THF）3

<正> (C6H5COCHCOC6H5)SmI2(THF)3,Mr= 843. 75,triclinic space group P1,a=13. 274(3),b=9. 886(3),c= 12. 526(4)A,a= 110. 89(3),B=93. 98(2),y=85. 16(2) ,V=1528. 9(8)A3,Z=2,Dc=1. 83g/cm3, (MoKa) = 0. 71069A,u= 40. 3cm-1,F(000) - 810. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R value of 0.082(Rw= 0. 083). The central Sm(III) ion is coordinated by two iodine ions, two oxygen atoms from C6H5COCHCOC6H5 and three oxygen atoms from three THF molecules to form a distorted pentagonal bipyramid. The Sm-I distances are 3. 103 and 3. 092 A ,The Sm-O (O atom from C6H5COCHCOC6H5) distances are 2. 273 and 2. 307 A and the average Sm -O(THF) distance is 2. 500A.     

SYNTHESIS AND CRYSTAL STRUCTURE OF DINUCLEAR IRON CARBONYL DERIVATIVE (μ-SC_6H_5) (μ-P (SC_6H_5)_2) Fe_2 (CO)_5 (P-(SC_6H_5)_3)

<正> The reaction of Fe3(CO)12 with P(SPh)3 yields the tile compound. C41H30Fe2O5P2S6, Mr = 968. 65, monoclinic, space group, P21/n, a = 14. 449(9), b = 18. 046(11), c=16.871(10)(?), β=98. 76°, V = 4348(?)3, Z = 4, Dc=1. 480g/ cm3, λ(MoKα) = 0. 71073(?) The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares procedure to R = 0.084, Rw = 0.144 for 4059 reflections. Fe(1)-Fe(2) = 2. 576(6), Fe(2)-P(2) = 2.194(9)(?). The dihedral angle between the Fe(l)SFe(2) and Fe(1)PFe(2) planes is 81. 9°. The other one (dihedral angle between SFe(1)P and SFe(2)P planes) is 75. 2°.     

Dihalogen(pentafluorphenyl)sulfonium(IV)-hexafluoroarsenat C6F5SX2+AsF6− (X = Cl,Br) und Kristallstruktur von Di(pentafluorphenyl)sulfan (C6F5)2S

Dihalogen(Pentafluorophenyl)sulfonium(IV) Hexafluoroarsenate C₆F₅SX₂⁺AsF₆^? (X = Cl, Br) and Crystal Structure of Di(pentafluorophenyl)sulfane (C₆F₅)₂S The preparation and spectroscopic characterisation of the halogensulfonium salts C₆F₅SCl₂⁺AsF₆^? and C₆F₅SBr₂⁺AsF₆^? is reported. The new salts are much more stable than their trifluoromethyl derivatives. In addition the crystal structure of (C₆F₅)₂S is reported. Space group P4₃2₁2, Z = 4, 478 unique observed diffractometer data, R_int. = 0.07, lattice constants: a = 569.0(5) pm, c = 3785.8(22) pm, V = 1225 times; 10^?30 m³.     

P5H6+和P5Me6+全反式构象的理论研究

用HF和MP2两种从头算方法结合cc-pVDZ和cc-pVTZ两种基组对P5H6 及其甲基取代物P5Me6 的反式构象进行理论计算,各限制优化出11个反式构象.进而分别得到其构象势能面曲线,P5H6 势能面曲线是单调平滑的,其上只有一个稳定点(3T4)和一个过渡态(4T3),说明3T4构象是势能面上的全局最小点.而P5Me6 势能面曲线与P5H6 大致相同,不同的是在势能面曲线中还存在另一个稳定点,在HF或MP2用cc-pVDZ基组时为2E(φ=216°),在HF/cc-pVTZ时为2T1(φ=198°),并且,3T4和2E的能量非常接近.最后将这两势能面与四氢呋喃进行了比较.     

X-ray crystal structure of (eta(5)-pentaphenylcyclopentadienyl)[1-(eta(5/6)-phenyl)-2,3,4,5-tetraphenylcyclopentadienyl]iron(II), [Fe(eta(5)-C(5)Ph(5))[(eta(5/6)-C(6)H(5))C(5)Ph(4)]], a linkage isomer of decaphenylferrocene

Very dark blue prismatic crystals of [Fe(eta(5)-C(5)Ph(5))[(eta(5/6)-C(6)H(5))(C(5)Ph(4))]], the linkage isomer of decaphenylferrocene, were grown from (3:1 v/v) hexane/ethyl acetate and characterized by single-crystal X-ray diffraction (space group P2(1)/n, R1(F) 0.0404). The iron atom is coordinated to two C(5)Ph(5) ligands: one with an eta(5)-C(5)-configuration and the other with a coordinated arene configuration. The phenyl groups of the (eta(5)-C(5)Ph(5)) ligand are oriented in a "paddle-wheel" arrangement about the C(5) ring, with which four of them make an average angle of approximately 53 degrees, the other, an angle of approximately 42 degrees. The coordinated C(6)H(5) ring of the other ligand is inclined at only approximately 5 degrees to the uncoordinated C(5) ring, with which three of the other four phenyl rings make an average angle of approximately 64 degrees, and the other (opposite the coordinated arene ring), an angle of 38 degrees.     

Cation-cation interactions in Sr5(UO2)20(UO6)2O16(OH)6(H2O)6 and Cs(UO2)9U3O16(OH)5

Two novel U6+ compounds, Sr5(UO2)20(UO6)2O16(OH)6(H2O)6 (SrFm) and Cs(UO2)9U3O16(OH)5 (CsFm), have been synthesized by mild hydrothermal reactions. The structures of SrFm (orthorhombic, C2221, a = 11.668(1), b = 21.065 (3), c = 13.273 A, V = 3532.5(1) A3, Z = 2) and CsFm (trigonal, R3c, a = 11.395(2), c = 43.722(7) A, V = 4916.7(1) A3, Z = 6) are rare examples of uranyl compounds that contain cation-cation interactions where an O atom of one uranyl ion is directly linked to another uranyl ion. Both structures are complex frameworks. SrFm contains sheets of polyhedra that are linked through cation-cation interactions with uranyl ions located between the sheets. CsFm possesses an unusually complex framework of vertex- and edge-sharing U6+ polyhedra that incorporates cation-cation interactions.     

Synthesis of (5R)- and (5S)-5-Methyl-5, 6-dihydrouridine Derivatives

The hydrogenation of 2′, 3′-O-isopropylidene-5-methyluridine (1) in water over 5% Rh/Al₂O₃ gave (5 R)- and (5 S)-5-methyl-5, 6-dihydrouridine (2) , separated as 5′-O-(p-tolylsulfonyl)- (3) and 5′-O-benzoyl- (5) derivatives by preparative TLC. on silica gel and ether/hexane developments. The diastereoisomeric differentiation at the C(5) chiral centre depends upon the reaction media and the nature of the protecting group attached to the ribosyl moiety. The synthesis of iodo derivatives (5 R)- and (5 S)- 4 is also described. The diastereoisomers 4 were converted into (5 R)- and (5 S)-2′, 3′,-O-isopropylidene-5-methyl-2, 5′-anhydro-5, 6-dihydrouridine (7) .     

Über die Kristallstruktur von (C6H5)3SiSH und (C6H5)3SiSBr und die Darstellung des Iodsulfans (C6H5)3SiSI

The Crystal Structure of (C₆H₅)₃SiSH and (C₆H₅)₃SiSBr and the Preparation of the Iodosulfane (C₆H₅)₃SiSI The preparation of the halogenosulfanes Ph₃SiSBr and Ph₃SiSI from Ph₃SiSH and N-halogenosuccinimide is reported. They are characterized by vibrational spectroscopic measurements. Ph₃SiSBr crystallizes in space group P1 with a = 899.3(8) pm, b = 941.3(7) pm, c = 1 051.4(7) pm, α = 109.88(5)°, β = 99.23(6)°, γ = 96.78(6)° and Z = 2. Ph₃SiSH crystallizes in space group P2₁/c with a = 1 879.4(8), b = 966.3(5), c = 1 845.2(9), β = 107.84(4), Z = 8. The halogenosulfanes decompose in polar solvents by formation of sulphur and triphenylsilanhalide.     

Synthese von (C6F5)2SF+MF6− (M  As,Sb) und Kristallstruktur von (C6F5)2SF+SbF6− [1]

Preparation of (C₆F₅)₂SF⁺MF₆^? (M ? As, Sb) and Crystal Structure of (C₆F₅)₂SF⁺SbF₆^? XeF⁺MF₆^? (M ? As, Sb) reacts with (C₆F₅)₂S in HF to form (C₆F₅)₂SF⁺MF₆^?. The deeply violet sulfonium salts can be kept without decomposition up to 24 h at room temperature. The hexafluoroantimonate salt crystallizes in the monoclinic space group P2₁/n with a = 1056.4(7) pm, b = 1446.3(10) pm, c = 1102.9(8) pm, β = 91.29(6)° und Z = 4. The SF-bond distance with 158.4(3) pm is of unusual length. Cations and anions are connected via interionic fluorine contacts to an infinite chain, in which cations and anions form to ABAB sequence along the chain.     

Oligomerization and oxide formation in bismuth aryl alkoxides: synthesis and characterization of Bi4(mu 4-O)(mu-OC6F5)6(mu 3-OBi(mu-OC6F5)3)2(C6H5CH3), Bi8(mu 4-O)2(mu 3-O)2(mu-OC6F5)16, Bi6(mu 3-O)4(mu 3-OC6F5)(mu 3-OBi(OC6F5)4)3, NaBi4(mu 3-O)2(OC6F5)9(THF)2, and Na2Bi4(mu 3-O)2(OC6F5)10(THF)2

Exposing [Bi(OR)3(toluene)]2 (1, R = OC6F5) to different solvents leads to the formation of larger polymetallic bismuth oxo alkoxides via ether elimination/oligomerization reactions. Three different compounds were obtained depending upon the conditions: Bi4(mu 4-O)(mu-OR)6(mu 3-OBi(mu-OR)3)2(C6H5CH3) (2), Bi8(mu 4-O)2(mu 3-O)2(mu 2-OR)16 (3), Bi6(mu 3-O)4(mu 3-OR)(mu 3-OBi(OR)4)3 (4). Compounds 2 and 3 can also be synthesized via an alcoholysis reaction between BiPh3 and ROH in refluxing dichloromethane or chloroform. Related oxo complexes NaBi4(mu 3-O)2(OR)9(THF)2 (5) and Na2Bi4(mu 3-O)2(OR)10(THF)2 (6) were obtained from BiCl3 and NaOR in THF. The synthesis of 1 and Bi(OC6Cl5)3 via salt elimination was successful when performed in toluene as solvent. For compounds 2-6 the single-crystal X-ray structures were determined. Variable-temperature NMR spectra are reported for 2, 3, and 5.     

Coordination chemistry of silver(I) with the nitrogen-bridged ligands (C(6)H(5))(2)PN(H)P(C(6)H(5))(2) and (C(6)H(5))(2)PN(CH(3))P(C(6)H(5))(2): the effect of alkylating the nitrogen bridge on ligand bridging versus chelating behavior

The coordination chemistry of silver(I) with the nitrogen-bridged ligands (C(6)H(5))(2)PN(R)P(C(6)H(5))(2) [R = H (dppa); R = CH(3) (dppma)] has been investigated by (31)P NMR and electrospray mass spectrometry (ESMS). Species observed by (31)P NMR include Ag(2)(mu-dppa)(2+), Ag(2)(mu-dppa)(2)(2+), Ag(2)(mu-dppa)(3)(2+), Ag(2)(mu-dppma)(2+), Ag(2)(mu-dppma)(2)(2+), and Ag(eta(2)-dppma)(2)(+). Species observed by ESMS at low cone voltages were Ag(2)(dppa)(2)(2+), Ag(2)(dppa)(3)(2+), Ag(2)(dppma)(2)(2+), and Ag(dppma)(2)(+). (C(6)H(5))(2)PN(CH(3))P(C(6)H(5))(2) showed a strong tendency to chelate, while (C(6)H(5))(2)PN(H)P(C(6)H(5))(2) preferred to bridge. Differences in the bridging versus chelating behavior of the ligands are assigned to the Thorpe-Ingold effect, where the methyl group on nitrogen sterically interacts with the phenyl groups on phosphorus. The crystal structure of the three-coordinate dinuclear silver(I) complex (Ag(2)[(C(6)H(5))(2)PN(H)P(C(6)H(5))(2)](3))(BF(4))(2) has been determined. Bond distances include Ag-Ag = 2.812(1) A, Ag(1)-P(av) = 2.492(3) A, and Ag(2)-P(av) = 2.509(3) A. The compound crystallizes in the monoclinic space group Cc at 294 K, with a = 18.102(4)(o), Z = 4, V = 7261(3) A(3), R = 0.0503, and R(W) = 0.0670.     

New class of ruthenium sulfide clusters: Ru(4)S(6)(PPh(3))(4), Ru(5)S(6)(PPh(3))(5), and Ru(6)S(8)(PPh(3))(6)

Reaction of RuCl(2)(PPh(3))(3) with S(2)(-) sources yields a family of phosphine-containing Ru-S clusters which have been characterized crystallographically and by MALDI-MS. Ru(4)S(6)(PPh(3))(4) (Ru-Ru(av) = 2.94 A) has idealized T(d)() symmetry whereas Ru(6)S(8)(PPh(3))(6) (Ru-Ru(av) = 2.82 A) adopts the idealized O(h)() symmetry characteristic of Chevrel clusters. Ru(5)S(6)(PPh(3))(5) is formally derived by the addition of Ru(PPh(3)) to one face of Ru(4)S(6)(PPh(3))(4). In terms of its M-S connectivity, the Ru(5)S(6) cluster resembles a fragment of the FeMo cluster in nitrogenase.     

Synthesis,structure and magnetic properties of {Mn5(OC(O)CH3)6(OC(O)C6H5)4}∞

The ligand exchange reaction between Mn(OC(O)CH₃)₂ and benzoic acid under solvothermal conditions in toluene at 110 °C yields colorless crystals of {Mn₅(OC(O)CH₃)₆(OC(O)C₆H₅)₄}_∞ (1). The asymmetric unit of this complex is Mn_2.5(OC(O)CH₃)₃(OC(O)C₆H₅)₂ with each of the three different Mn(II) atoms in 6-fold coordination and one of the benzoate ligands exhibiting the rare μ₃-symmetric bridging mode (O–Mn–O angle = 57°). The structure consists of edge-shared Mn₁₂ loops arranged in a honeycomb-like 2D sheet with the acetate ligands displaced slightly out of the plane. The sheets are spaced at 12 Å and linked into a 3D network via weak intersheet interactions. Magnetic susceptibility characterization of 1 indicates antiferromagnetic exchange with a Weiss constant of −165 K and a transition toward ferromagnetic exchange below 10 K corroborated with a finite imaginary component in the variable temperature susceptibility data.     

Tropochemical cell-twinning in the new quaternary bismuth selenides KxSn(6-2x)Bi(2+x)Se9 and KSn5Bi5Se13

The quaternary K(x)Sn(6-2x)Bi(2+x)Se(9) and KSn(5)Bi(5)Se(13) were discovered from reactions involving K(2)Se, Bi(2)Se(3), Sn, and Se. The single crystal structures reveal that K(x)Sn(6-2x)Bi(2+x)Se(9) is isostructural to the mineral heyrovskyite, Pb(6)Bi(2)S(9), crystallizing in the space group Cmcm with a = 4.2096(4) A, b = 14.006(1) A, and c = 32.451(3) A while KSn(5)Bi(5)Se(13) adopts a novel monoclinic structure type (C2/m, a = 13.879(4) A, b = 4.205(1) A, c = 23.363(6) A, beta = 99.012(4) degrees ). These compounds formally belong to the lillianite homologous series xPbS.Bi(2)S(3), whose characteristic is derivation of the structure by tropochemical cell-twinning on the (311) plane of the NaCl-type lattice with a mirror as twin operation. The structures of K(x)Sn(6-2x)Bi(2+x)Se(9) and KSn(5)Bi(5)Se(13) differ in the width of the NaCl-type slabs that form the three-dimensional arrangement. While cell-twinning of 7 octahedra wide slabs results in the heyrovskyite structure, 4 and 5 octahedra wide slabs alternate in the structure of KSn(5)Bi(5)Se(13). In both structures, the Bi and Sn atoms are extensively disordered over the metal sites. Some physicochemical properties of K(x)Sn(6-2x)Bi(2+x)Se(9) and KSn(5)Bi(5)Se(13) are reported.     

Specificity in template syntheses of hexaaza-macrobicyclic cages: [Pt(Me5-tricosatrieneN6)]4+ and [Pt(Me5-tricosaneN6)]4+

The racemic C3 hexadentate cage complex, [Pt(Me5-tricosatrieneN6)]Cl4 (1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]tricosa- 3,14,18-triene)platinum(IV) tetrachloride), was synthesised stereospecifically and regiospecifically from a reaction of the bis-triamine template [Pt(tamc)2]Cl4 (bis[1,1,1-tris(aminomethyl)ethane]- platinum(IV) tetrachloride) with formaldehyde and then propanal, in acetonitrile under basic conditions. Largely, one racemic diastereoisomer was obtained in a surprisingly high yield (approximately 50%), even though the molecule has seven chiral centres. The origins of the stereoselective synthesis are addressed. The crystal structure of [Pt(Me5-tricosatrieneN6)]-(ZnCl4)1.5Cl.2H2O showed that all three imines were attached to one tame fragment with a chiral amine site ([symbol: see text] SSS, delta RRR) and a chiral methine carbon site ([symbol: see text] RRR, delta SSS) on each ligand strand. The PtN6(4+) moiety had a slightly distorted octahedral configuration with the two types of Pt-N bonds related to the imine and the amine donors, 2.050(7) and 2.072(6) A, respectively. Treatment with sodium borohydride (15 s, 20 degrees C) at pH approximately 12.5 reduced the imine groups, but not the Pt(IV) ion, producing a C3 saturated ligand complex [Pt(Me5-tricosaneN6)]Cl4 ((1,5,9,13,20- pentamethyl-3,7,11,15,18,22- hexaazabicyclo[7.7.7]tricosane)platinum(IV)tetrachloride). X-ray crystallographic analysis showed that the average Pt-N bond distance in the cation increased upon imine reduction to 2.10 (av) A. The cyclic voltammograms of the two cage complexes displayed irreversible two-electron reduction waves in aqueous media and a approximately 0.3 V shift to more positive potentials compared to that of the smaller cavity sar (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) analogue. After reduction, net dissociation of one strand of the cage was also evident, to give unstable square planar Pt(II) macrocyclic products.     

Characterization and reactions of previously elusive 17-electron cations: electrochemical oxidations of (C(6)H(6))Cr(CO)(3) and (C(5)H(5))Co(CO)(2) in the presence of [B(C(6)F(5))(4)](-)

The electrochemical oxidations of (C6H6)Cr(CO)3, 1, and (C5H5)Co(CO)2, 2, when carried out in CH2Cl2/[NBu4][B(C6F5)4], allow the physical or chemical characterization of the 17-electron cations 1+ and 2+ at room temperature. The generation of 1+ on a synthetic time scale permits an electrochemical "switch" process involving facile substitution of CO by PPh3 as a route to (C6H6)Cr(CO)2PPh3. The radical 2+ undergoes a second-order reaction to give a product assigned as the metal-metal bonded dimer dication [Cp2Co2(CO)4]2+. The new anodic chemistry of these often-studied 18-electron compounds is made possible by increases in the solubility and thermal stability of the cation radicals in media containing the poorly nucleophilic anion [B(C6F5)4]-, TFAB.     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

Dihydrogen activation with (t)Bu3P/B(C6F5)3: a chemically competent indirect mechanism via in situ-generated p-(t)Bu2P-C6F4-B(C6F5)2

A chemically competent indirect pathway for the activation of dihydrogen by the nonmetal Lewis acid/Lewis base pair (t)Bu(3)P/B(C(6)F(5))(3) is described. The reaction between (t)Bu(3)P and B(C(6)F(5))(3) produces [(t)Bu(3)PH](+)[FB(C(6)F(5))(3)](-) and the known phosphinoborane p-(t)Bu(2)P-C(6)F(4)-B(C(6)F(5))(2) (1-(t)Bu) with elimination of isobutylene. At 1:1 stoichiometry, 1-(t)Bu is produced rapidly in detectable quantities and can act as a catalyst for the formation of [(t)Bu(3)PH](+)[HB(C(6)F(5))(3)](-) from (t)Bu(3)P and B(C(6)F(5))(3) in the presence of H(2). The extent to which this indirect path competes with the direct path is explored.     

6(5H)-phenanthridinones. III. halo-6(5H)phenanthridinones

Halogenation of 6(5H)-phenanthridinone or its 3,8-dihalo derivatives with N-bromo or N-chlorosuccinimide in dimethylformamide gives the corresponding 2-halophenanthridinones (I,V,XI-XIV). Further halogenation of 2-halo-6(5H)-phenanthridinone with the appropriate N-halosuccinimide, in the same medium, gives the corresponding 2,4-dihalo derivatives (II,VI). NXS/DMF is found to be a very convenient halogenating system in these preparations. 1,3,8-Trihalo-6(5H)-phenanthridinones (XIX,XX) are prepared from the 1-nitro derivatives which are obtained by a Schmidt rearrangement of 2,7-dihalo-4-nitro-9-oxofluorenes. Similarly, rearrangement and further reaction of 2-nitro-5-chloro-9-oxofluorene (XXI) leads to 3,10-dichloro-6(5H)-phenanthridinone (XXIV). UV absorptions as well as selected IR absorptions of these 6(5H)-phenanthridinones are described.