THE STUDY OF SPECTRA AND X-RAY CRYSTAL STRUCTURE OF A NOVEL BIONICS INSECTICIDE——(CH_3)_2NHCH(CH_2S_2O_3)_2Na·H_2O

IR and NMR spectra of novel bionics insecticide—C_5NS_4O_6H_(12)Na·H_2O have been studied. The molecular and crystal structures of the compound also have been determined. The compound crystallizes in the monoclinic space group C_(2h)~5, - P2_1/n with α= 8.0972. (9) , b =16.262(4), c = 10.370(3), β= 94.26(2)° and z = 4.The result shows that N atom in this compound captures a proton to form HN~ group, Na~ is in statistical disorder. Therefore, the structural formula of tho compound is (CH_3)_2HN~ —CH(CH_2S_2O_3~-)_2·1/2 (Na~ )_2·H_2O.     

STUDIES ON ORGANOMETALLIC COMPOUNDS OF TITANIUM,ZIRCONIUM AND HAFNIUM——THE SYNTHESES AND PROPERTIES OF BIS (CYCLOPENTADIENYL) AND BIS (METHYLCYCLOPENTADIENYL) DI(ARYL)-METAL DERIVATIVES

Aryllithium reacts with Cp_2MCl_2 and Cp'_2 MCl_2 (C_p=η~5-C_5H_5, C_P′=η~5-CH_3C_5H_4:M=Ti, Zr, Hf) respectively to prepare a series of new bis (cyclopentadienyl), bis (methy-lcyclopentadienyl) diaryl derivatives of titanium, zirconium and hafnium. The hydrolysicreaction of these organometallic compounds are studied, the derivatives of zirconium andhafnium can be easily hydrolyzed with the exception of that of titanium. They react withhydrogen chloride, acetyl chloride, bromine and haloacids to form the respective bis(cyclo-pentadionyl) dihalides of these metals. The NMR and IR spectra were discussed in regardto the structure of (η~5--CH_3C_5H_4)_2 MAr_2 and (η~5--CH_3C_5H_4)_2 MX_2.     

SYNTHESIS AND CRYSTAL STRUCTURE OF TWO NOVEL CARBENE AND CARBYNE COMPLEXES OF RHENIUM

The cationic carbyne complex of rhenium, [π-C_5H_5(CO)_2ReCC_6H_5] BBr_4(Ⅰ), in tetrahy-drofuran reacted with 1-lithiocarborane at low temperature, with addition of the carbo-ranyl anion to earbyne earbon and carbonyl carbon atoms to give two novel carbene andcarbyne complexes of rhenium, π-cyclopentadienyl (dicarbonyl) [(1-earboranyl) (phenyl)carbene] rhenium π-C_5H_5 (CO)_2ReC (C_2HB_(10)H_(10)) C_6H_5, (Ⅱ) and π-cyclopentadienyl-(carbonyl)(1-carboranylformacyl) (phenylcarbyne) rhenium π-C_5H_5 (CO) (COC_2HB_(10)H_(10)) ReCC_6H_5 (Ⅲ).This fact indicates that there are two electrophilic centers in the cationic carbyne complexⅠ. At room temperature the complex Ⅲ in solution transformed gradually into the complexⅡ. The complexes Ⅱ and Ⅲ were identified by elemental analyses, IR, ~1H NMR and massspectra, and finally by their single crystal X-ray structure determinations. The possiblereaction mechanism is suggested and discussed in this paper.     

UV LASER INITIATED STEREOSELECTIVE HOMOGENEOUS CATALYSIS POLYMERIZATION OF PHENYLACETYLENE

In this paper, the stereoselective homogeneous catalysis polymerization of phenylacetylene by using two kinds of catalysts W(CO)_5CH_3I and W(CO)_4I_2 produced from UV laser photolysis of W (CO)_6 in CH_3I, I_2—C_6H_6 and CHI_3—C_6H_6 respectively was studied. The effects of laser energy, laser irradiation time and lifetime of catalyst on the polymerization of phenylacetylene were discussed. The photoproducts of W (CO)_6 in CH_3I, I2—C_6H_6 and CHI_3—C_6I_6 were determined by IR spectra. The structures of polyphenylacetylene obtained by W (CO)_5CH_3I and W (CO)_4I_2 catalysts were characterized by IR spectra and ~1H NMR spectra.     

STRUCTURE AND CATALYTIC ACTIVITY OF RHODIUM COMPLEX COORDINATED ON 2-VINYLPYRIDINE-METHYL ACRYLATE COPOLYMER FOR THE CARBONYLATION OF METHANOL

A series of rhodium complexes coordinated on the hybrid ligand. 2-vinylpyridine-methyl acrylate copolymers, as catalyst for the carbonylation of methanol were synthesized by the reaction of the copolymers with tetracarbonyldichlorodirhodium. These complexes were in general very reactive in carbonylation of methanol to form acetic acid and methyl acetate without other by-product. The XPS studies of the complexes showed that the binding energies of Nls(399.1-399.4 eV) and that of Ols(532.5-532.9 eV) were higher than that of the copolymer ligand (Nls 398.1-398.3 eV and Ols 532.2-532.3 eV), indicating the fromation of N→Rh and O→Rh coordination bonds. The IR spectra of complexes showed that the appearance of two absorption peaks of terminal carbonyl at 1990-2100 cm~(-1), characteristic of the cis-dicarbonyl rhodium moiety. These XPS and IR studies confirm the formation of cis-dicarbonylrhodium complex with the active centers(A) and (B) as shown in the text. The increase of activity of the complex in the c     

STUDIES ON SYNTHESIS, STRUCTURE AND PROPERTIES OF THE CRYSTAL OF TRIADIC COMPLEX {Mo[S_2CN(C_2H_5)_2]_4}~( 1){FeCl_4}~(-1){C_6H_5CH_2SSCH_2C_6H_5}

In this paper, a new complex {Mo[S_2CN(C_2H_5)_2]_4}~( 1){FeCl}~(-1){C_6H_5CH_2SSCH_2C_6H_5} is syn-thesized by the reaction of MoCl_5, FeCl_3, PhCH_2SH and diethyldithiocarbamate (DTC)in MeOH. The complex is characterized by X-ray, IR, UV-visible, reflection spectra, themeasurements of magnetic susceptibility, differential thermal and elemental analyses. The crystal of triadic complex containing multi-bond species is quite stable and rare.     

THE CRYSTAL STRUCTURE OF A NOVEL INCLUSION COMPOUND——TETRAKIS

The title compound crystallizes in the space group C_5~4 with unit cell constants a=17.900 (5)A, b=18.466 (7)A, c=15.483 (4)A, β=92.78 (2)°and contains four formulaunits of MoFeS_(10)Cl_4N_4C_(34)H_(54). Intensities of 3499 independent reflections are collected withdiffractometer using MoKa radiation. The y coordinates of the Mo atoms are derived fromthe Patterson function. The parameters of the other atoms are found from successive Fourierand difference syntheses. The block-diagonal least-squares refinement for all atoms gives a final discrepancy factorR = 0.054. The result of structure analysis shows that this inclusion compound consists of threekinds of structural units and the oppositely charged complex ions [Mo(S_2CN(Et)_2)_4]~ and[FeCl_4]~- form a very interesting ionic host framework with infinite tunnels extending alongC direction and containing guest disulfide molecules PhCH_2SSCH_2Ph.     

CRYSTAL STRUCTURE INVESTIGATION OF VANADYL COMPLEXES OF TRIDENTATE LIGAND (Ⅱ)——SYNTHESE AND CRYSTAL STRUCTURE OF 1-(2-PYRIDYLAZO)-2-NAPHTHOLATO-DIOXOVANADIUM (Ⅴ) DIMER [VO_2(C_(15)H_(10)N_3O)]_2(H_2O_2)(CHCl_3)_2 AND PYRIDINE-(1-(2-PYRIDYLAZO)-2-NAPH

The title complexes crystallize in space groups C(?)-P(?) and C_(2h)~5-P2_1/c, and with unit cell parameters a=8.488. b=10.100, c=11.974. α=72.73°, β=78.56°, γ=73.55°, and a=11.496, b=9.883. c=16.360, β=100.18°, respectively. All the V coordinates are obtained from Patterson and direct methods, respectively, and then Fourier and difference Fourier methods are employed to deduce other non-hydrogen atoms. Structural parameters are refined with least-squares technic, yielding final discrepancy factors R=0.081 and 0.067, respectively. Structural analyses demonstrate that the dimer of VO_2~+ complex is formed through the sixth-position bonding of a bridge oxygen atom of one VO_2~+ group with another VO_2~+, and the formation of VO(O_2)(C_(15)H_(10)N_3O)(C_5H_5N) shows that VO~(2+) complex with strong chelating tridentate PAN-seems less difficult to transform into the pentagonal bipyramid VO~(3+) complex. Since no peroxo species has been used in the synthesis, the fact that a peroxo group forms in the     

SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION

By treating disodium(thiophenedirnethylene)dicyclopentadienide C_4H_2S(CH_2C_5H_4Na)_2 with two equivalent of CpTiCl_3 or CpZrCl_3 DME at 0℃ in THF,two new thiophenedimethylene bridged binuclear metallocenes [Cl_2MC_5H_5][C_5H_4CH_2C_4H_2SCH_2C_5H_4][C_5H_5MCl_2](M=Ti 3,M=Zr 4)were synthesized in high yield and their structures were characterized by ~1H-NMR.These complexes were used as catalysts for ethylene polymerization in the presence of methylaluminoxane(MAO).The effects of polymerization temperature,time,concentration of catalyst,molar ratio of MAO/Cat on polymerization were studied in detail.The catalytic activities of thiophenedimethylene bridged binuclear metallocene catalysts(3,4)reached 2.44×10~5 g PE mol~(-1)·cat~(-1)·h~(-1),9.61×10~5 g PE mol~(-1)·cat~(-1)·h~(-1) respectively,which are higher than that of pheneyldimethylene bridged binuclear metallocene catalysts and much higher than that of corresponding mononuclear metallocenes(Cp_2TiCl_2 and Cp_2ZrCl_2).The molecular weight distribution curves of polyethylenes produced by binuclear metallocene catalysts(3,4)and by mononuclear metallocene catalyst have only single peak,but the former(MWD=3.5-4.7)is obviously broader than the latter(MWD=2.0-2.2).     

THE CRYSTAL STRUCTURE OF THE ADDITION COMPOUND OF DECAVANADIC ACID AND 5,7-DIMETHYL-2, 3-DIHYDRO-1, 4-DIAZEPINIUM

The title compound crystallizes in the space group C_(2h)~5-P2_1/n with unit cell constantsa=10.938 A, b=19.189 A, c=13.384 A and β=105.09°. Intensities of 4022 independent reflec-tions were collected with four-circle diffractometer using MoKa radiation. After reduction fordiffractometer data, we derived first the position parameters of all the V atoms by directmethod using SHELXTL program. The coordinates of all the non-hydrogen and hydrogenatoms were obtained from successive Fourier and difference sytheses. The block-diagonalleast-squares refinement for all atoms gave a final discrepancy weighted factor R_w=0.050. The result of structure analysis shows that four protons of each decavanadic acid arecaptured by the nitrogen atoms involved in the azepine molecules which are condensation pro-ducts of ethylenediamine with acetylaceton. In crystal, the isopoly-decavanadate anion, 7-member heterocyclic azepium and the crystal water are linked together by ionic forces andhydrogen bonding and the chemical content within a unit cell has been identified as 2[H_2V_(10)O_(28)]~(-4)·8[C_7N_2H_(13)]~( 1)·12H_2O.     

Synthesis,Structure and Slow Magnetization Relaxation of Co(Ⅱ) Complexes from a Flexible Imidazole-based Ligand

The employment of a flexible imidazole-based ligand(H_2L), condensed from 1 Himidazole-2-carbaldehyde and 1,2-bis(aminooxy)ethane, and Co~(2+) salt has led to the formation of Co(Ⅱ) complexes [Co(H_2L)_2Cl]Cl·4CH_3OH(1) and [Co(H_2L)(NCS)_2]_2·2C_4H_(10)O(2), in the presence of different anions, i.e, Cl-and SCN-, respectively. Single-crystal X-ray analyses show that complex 1 with a square pyramid(C_(4v)) local environment exhibits a two-dimensional(2D)layered(4,4)-net framework and complex 2 displays a dinuclear molecule box with a T_d local environment. By comparison between complexes 1 and 2, the versatile configuration of ligand including cis-and trans-form isomer has a significant effect on the structures of the resulting complexes. The magnetic properties of 1 and 2 are also investigated. The ac magnetic susceptibility revealed that 2 exhibits the characteristic of slow magnetization relaxation.     

STUDY ON THE STRUCTURE AND SPECTRA OF BINUCLEAR BRIDGED COMPLEX μ-4,4-bipy [VO(acac)_2]_2

The synthesis and ~1H NMR, ESR, IR, UV spectra of binuclear bridged complex μ-4,4-bipy[VO-(acac)_2]_2 are reported in this paper. The structure of the complex is discussed using measured spectral parameters.It is deemed that 4,4-bipy as a bridge passing through its two N atoms combined respectively with two V atoms at its sixth position, forming a binuclear bridged complex.The spectra are explained satisfactorily and coefficients of molecular orbitals,β_1,β_2 and 8_m,are calculated from the results of ESR and UV etc.     

NdCl_3/MgCl_2 BISUPPORTED CATALYST FOR OLEFIN POLYMERIZATION

The NdCl_3/MgCl_2 bisupported catalyst was prepared by using NdCl_3 ,MgCl_2, (CH_3)_2(CH_2)_2 OH and TiCl_4. It is shown that the structure of bisupported catalyst was different from those of either NdCl_3 or MgCl_2 single supported catalyst. A peculiar type of kinetic curve for ethylene polymerization was found.     

TiCl_4,MgCl_2和酯络合物的晶体结构和光谱性质——Ziegler-Natta高效聚丙烯催化剂结构研究之一

本文研究了直接有工业意义的TiCl_4、MgCl_2和酯络合物的晶体结构,并测定了粉末图,红外和紫外光谱。TiCl_4和PhCOOEt(L)生成(TiCl_4·L)_2和TiCl_4·2L两种络合物。MgCl_2与CH_3COOEt和H_3O形成MgCl_2·2CH_3COOEt·2H_2O络合物。这些分子间靠范德瓦力结合成晶体。相应的空间群分别为C_(2h)~5—P2_1/c,C_(2h)~5—P2_1/n和C_(2h)~5—C2/c。利用所得粉末图证实了研磨浸渍法制备催化剂过程中确有(TiCl_4·L)_2生成。对比高效催化剂和Mg络合物的红外光谱,表明催化剂表面络合物的配键与络合物相似。     

SOLUBLE POLYACETYLENE OBTAINED WITH RARE-EARTH CATALYST AND SOME ASPECTS OF POLYMERIZATION MECHANISM

Soluble polyacetylene (PA) with well--defined nature has been synthesized with catalyst system Nd(i-OPr)_3/AIR_3 (R=C_2H_5-, i-C_4H_9-) and characterized by IR, Raman and ESR Spectra etc. Number average molecular weight of the soluble specimen were determined by VPO to be about 500g/mol. or lower. The IR and NMR spectra and end group analysis of" the soluble polyacetylene fully demonstrate that polymerization of acetylene with rare-earth catalyst is realized through monomer insertion between the transition metal-carbon bond.     

STUDIES ON TiCI4/Mg (OEt)_2/EB SUPPORTED CATALYSTS FOR PROPYLENE POLYMERIZATION

The supported catalysts for propylene polymerization were prepared by milling Mg (OEt)_2 with EB (ethylbenzoate) and treating with TiCl_4 solution. When TiCl_4/(Mg(OEt)_2/EB) (mol.) ratio was increased, decrease in contents of-OEt and Ti of the catalysts was observed, while the content of EB increased. It is proved by analyses of IR, X-ray and XPS that during co-milling Mg(OEt)_2 with EB no reactions have taken place. But after treatment with TiCl_4 solution, Mg(OEt)_2 converts into MgCl_2 and EB coordinates on the resulting MgCl_2 carrier, a surface complex forms.The activity of catalysts,isotacticity and vicosimetric molecular weight of polypropylene increase with the decrease of the content of ethoxyl group. The kinetic curves of propene polymerization obtained with present catalysts system display decay curves. It is found from the triad tacticity calculated from the expanded spectra of methyl carbon region that, ethoxyl group in catalyst has an effect on the configuration of polymer chain.     

PREPARATION AND X—RAY CRYSTAL STRUCTURE OF [(C_6H_5)_2PCH_2CH-2P(C_6H_5)_2]Fe(NO)_2

The complex [(C_6H_5)_2PCH_2CH_2P(C_6H_5)_2]Fe (NO)_2, was easily synthesized by the reaction of Fe (CO)_5, NaNO_2 and (C_6H_5)_2PCH_2CH_2P(C_6H_5)_2 (dppe) in methanol and determined by X—ray diffraction which denoted that the title complex has two crystallographically independent molecules in its asymmetric unit.     

PREPARATION AND CRYSTAL STRUCTURE OF TETRAMETHYLETHENE-BRIDGED DICYCLOPENTADIENYLSAMARIUM (Ⅲ) COMPLEX

(CH_3)_4C_2(C_5H_4)_2Sm(C_5H_5)OC_4H_, Mr=499.4, orthorhombic, Cc2a, a=11.696(6), b=12.539(5), c=29.432(15), V=4316(4)~, Z=8, Dc=1.54g. cm~(-3), μ (MoKα)=27.8cm~(-1), F(000)=2024, R=0.077 for 1833 observed reflections. In the molecule the samarium atom is bonded to three cyclopentadienyl rings and an oxygen of tetrahydrofuran(THF). The three centroids of the cyclopentadienyl rings and the oxygen form a tetrahedral configuration around the Sm(Ⅲ) atom, The average Sm-C(η~) bond distances for the three cyclopentadienyl groups are 2.72(3), 2.76(3), 2.78(8) respectively, and Sm-0 bond is 2.53(1).     

STUDY ON THE MECHANISM OF 1-OCTENE ZIEGLER-NATTA POLYMERIZATION BASED ON THE NUMBER OF ACTIVE CENTERS

The number of active centers (C_p)-t and k_p-t profiles of Solvay type TiCl_3 - AlR_3 (R=C_2H_5, i-C_4H_9) or Stauffer AA TiCl_3-Al (C_2H_5)_3 catalyzed 1-octene polymerization were determined by using an acetyl chloride quenching method as well as kinetic data. The results show that in the studied systems k_p decreases when C_p increases, indicating the presence of two or more types of different active centers. The C_(p~(-t)) plots of the Solvay TiCl_3-AlR_3 systems show the presence of both stable active centers and unstable centers which decay in the polymerization process. The phenomena are explained based on a model of active center plurality. The increases of C_p in the induction periods are also discussed.     

THE ESR STUDY OF SOME DICYCLOPENTA-DIENYL TITANIUM HALIDE COMPLEXES

The ESR spectra of some [Cp_2Ti(L)X] complexes (Cp: C_5H_5, MeC_5H_4; L: phosphane,isocyanide, pyridine, amine and carbon monoxide; X: F, Cl, Br, I) have been obtained.When X is Cl, Br or I, the linear relationships between the g value and hyperfine couplingcoustant a(Ti) are explained in terms of the electron character of the L ligand and the ESRspectral trends of the complexes are studied.