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

The dichlorides of bis(cyclopentadienyl) or bis(methylcyclopentadienyl) titanium, zircon-ium and hafnium reacting with phenol or substituted phenols in the presence of base give aseries of new aryloxymetal derivatives. The activities of chlorine atoms in the dichlorides ofbis(cyclopentadienyl)titanium, zirconium and hafnium molecules towards phenols are compared.The influence upon HNMR of the cyclopentadienyl ring due to the electronegativities of themetals and the substituents on the phenyl rings, as well as the number and position of thesubstituents are discussed.     

STUDIES ON BIS(ALKENYLCYCLOPENTADIENYL) IVB GROUP METAL DERIVATIVES

A series of new bis(allyleyclopentadienyl) and bis(2-butenylcyelopentadienyl) dichlorides of titanium, zirconium and hafnium have been synthesized by reacting sodium allyl or 2-butenylcyclopentadienide with IVB group metal chlorides. The substituted bis-cyclopentadienyl metal dichlorides treated with inorganic halides, aryllithium, potassium thiocyanate or hydrogen sulfide, bis(alkenylcyclopentadienyl)metal dihalides, and that of diaryl, dithiocyanato and dimercaptometal derivatives were obtained. Addition reaction on allyl group in bis(allylcyclopentadienyl) dihalides of titanium, zirconium and hafnium with hydrogen halide, halogen was studied. It was found that the addition of HX followed Markovnikov's rule.The reactivity of electrophilic addition increased in the order HCl相似文献   

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori     

SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURES OF η~5-CH_3C_5H_4)M(CO)_2NO AND(η~5-CH_3C_5H_4)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo or W)

Synthesis of complexes(η~5-CH_3C_5H_4)M(CO)_2NO(M=Mo,I;M=W,II)and clusters(η~5-CH_3C_5H_4)M(μ~3-NH)(μ~2-NO) (μ~2-CO)Fe_2(CO)_6(M=Mo,III:M=W,IV),based on the reaction of (η~5-C5_H_4)M(CO)_3Cl with Na[Fe(CO)_3NO] at room tem-perature,have been demonstrated,The crystal structures of II and IV arealso presented.     

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).     

Synthesis, Reaction and Structures of Functionally Substituted η~5-Cyclopentadienyl Compounds With Cr≡S Triple Bond [η~5-RC_5H_4Cr(CO)_2]_2S (R=CH_3C(O),CH_3O_2C,C-2H_5O_2C,CH_3CH(OH),CO_2H)

[η_5-OH_3C(O)C_5H_4Cr(CO)_2]_2S 1, [η~5-CH_3O_2CC_5H_4Cr(CO)_2]_2S 2 and [η~5-C_2H_5O_2CC_5H_4Cr(CO)_2]_2S 3 were prepared by the reactions of corresponding sodium salts of functional η~5-cyclopentadienyl-tricarbonylchromium anions with SOCl_2. Reduction of 1 with NaBH_4 prdouced [η~5-CH_3CH(OH)C_5H_4Cr(CO)_2]_2S 4, while saponification of 2 followed by acidification and recrystallization from acetone afforded [η~5-HO_2CC_5H_4Cr(CO)_2]_2S·nCH_3C·(O)CH_3 5. 1—5 are a new class of Cr≡S triple bond compounds containing functional organic group on the cyclopentadienyl ring. A single-crystal X-ray diffraction analysis of 1 revealed that it consists of two identical organometallic fragments η~5-CH_3C(O)C_5H_4Cr(CO)_2 joined together by a sulfur atom via triple bonds. The geometry of structural unit Cr≡S≡Cr belongs to linearity and the average triple bond length of Cr≡S is 2.072(?).     

STUDIES ON cis-trans-ISOMERIZATION AND REACTION KINETICS OF A μ, η~2-VINYL LIGAND IN A TRIOSMIUM CLUSTER

The dihydride cluster H_2O_(s_3)(CO)_(10) reacts with ethyne to give a cis-adduct [O_(s_3)H(μ,η~2-CH=CH_2)(CO)_(10)]. The high deuterated cluster D_2O_(s_3)(CO)_(10), the reaction of D_2O_(s_3)(CO)_(10)with ethyne C_2H_2 to form the vinyl product cluster [O_(s_3)D(μ, η~2-CH=CHD)(CO)_(10)], and thereaction of H_2O_(s_3)(CO)_(10) with the deuterated ethyne C_2D_2 to form [O_(s_3)H(μ,η~2-CD=CDH)(CO)_(10)] have been reported primarily in this paper. The two cis-adducts undergo cis-trans-isomerization of μ,η~2-vinyl ligands under a small amount of the nucleophile pyridine. Usingthe combination of deuteration and dynamic ~1H,~2H NMR spectra, we report the experimen-tal evidence determined by the dynamic ~1H, ~2H NMR spectra, mechanism, and kinetic dataof the isomerization.     

SYNTHESIS, SPECTRAL AND MAGNETIC CHARACTERISATION OF SOME BIMETALLIC ALKOXIDES OF NICKEL(Ⅱ)WITH GALLIUM(Ⅲ)AND ZIRCONIUM(IV)

Some interesting bimetallic isopropoxides of nickel(Ⅱ) with gallium(Ⅲ) and zirconium(Ⅳ), Ni[Ga(OPr~1)_4]_2 and Ni[Zr_2(OPr_1)_9]_2 have been synthesized by the interaction of NiCl_2·2Pr~1OH with K[Ga(OPr~1)_4],and K[Zr_2(OPr~1)_9] respectively, in 1:2 molar ratio. These bimetallic isopropoxides undergo facile alcohol interchange reactions with primary alcohols. However, reactions with tertiary alcohols result in the isolation of partially substituted derivatives with the compositions, Ni[Ga(OPr~1)(OBu~t)_3]_2 and Ni[Zr_2(OPr~1)_3(OBu~t)_6]_2. Characterisation of these derivatives has been made on the basis of elemental analyses, infrared, electronic spectral and magnetic susceptibility measurements. These studies suggest an octahedral geometry for nickel(Ⅱ) in the primary bimetallic alkoxides, while in the case of secondary and tertiary derivatives, an equilibrium is suggested between octahedral and tetrahedral forms.##属性不符     

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 CRYSTAL AND MOLECULAR STRUCTURES OF OXO-BRIDGED TETRAKIS(CYCLOPENTADIENYL)BIS (o.TOLYL)AND TETRAKIS(METYLCYCLOPEN-TADIENYL) BIS(p-TOLYL)BINUCLEATED ZIRCONIUM COMPOUNDS

This paper reports the crystal and molecular structures of tetrakis (cyclopentadienyl) bis(o-tolyl)-μ-oxo-dizirconium [dimer (Ⅰ)] and tetrakis (methylcyclopentadienyl) bis (p-tolyl)-μ-oxo-dizirconium [dimer (II)]. Both of them belong to monoclinic system and possess the same spacegroup C_2~5h- 2_1/a. The cell dimer (Ⅰ) containing four molecules is defined by a=19.122A,b=16.319A, c = 9.296A, β= 92°1′; the cell dimer (Ⅱ) containing two molecules is defined bya = 20.076A, b = 8.205A, c = 10.016A, β= 104°41′. The important difference of molecular configurations between the two dimers lies in thatthe dimer (Ⅰ) has no symmetry center and its Zn-O-Zr oxo-bridge presents a slightly bentconfiguration while the dimer (Ⅱ) takes the oxgen atom as a symmetry center and its oxo-bridge present linear linkage. In accordance with the above-mentioned molecular configuration, steric effect and elec-tronic structure have been further discussed.     

THE FORMATION AND CRYSTAL STRUCTURE OF (η~5-C_5H_5)_3Nd·OC_4H_8 AND (η~5-C_5H_5)_3Pr·OC_4H_8

Under suitable reactant ratios without sublimation or reerystallization, single crystals of(η~5-C_5,H_5)_3 Ln-OC_4H_8(In = La, Pr, Nd) could be prepared by the reaction of cyclopentadienylsodium with respective lanthanide trichlorides in THF. Using low temperature technique wehave collected the X-ray data of single crystals of the title compounds at -60℃ under N_2and determined crystal structures. (η~5-C_5H_5)_3 Pr·OC_4H_8, [(η_5-C_5H_5)_3 Nd·OC_4H_8] recrystallizesin the monoclinic space group P2_1/n[P2_1/n] with unit cell parameters a = 8.406(3) [8.364(3)],b = 24. 510(9) [24.467(9)], c = 8. 284(3) [8.254(3)] A, β= 101.60(3) [101.42 (3)], D_c = 1. 62 [1.65]gem~(-3) for z = 4 [4]. Least-square refinement has led to a final R value of 0.056 [0.063],R_W = 0.049 [0.062]. The THF molecule is coordinated to the Pr [Nd] atom at a Pr-O [Nd-O]bond length of 2.16(1) [2.54(1)], A. The Pr-C (Cp) [Nd-C(Cp)] bond distances average 2.80(2) [2.78(2)] A. The title compounds are isostructaral with (η~5-C_5H_5)_3     

SYNTHESIS of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF AND CRYSTAL STRUCTURE OF(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF

The reaction of LnCl_3 with K _9H_7(C_9H_7=indenyl)andK_2C_8H_8(C_8H_8=cyclooctatetraene)in tetrahydrofuran(THF)give thecorresponding complexes(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF.The synthesis of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF(Ln=Pr,Nd)and crystal structure of(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF are described.     

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.     

IR AND EPR STUDIES OF THE NUCLEAR ALKYLATION OF TOLUENE AND ETHYLENE ON THE MODIFIED Mg—AND P—ZSM—5 CATALYST

The surface intermediate (C_2H_5~+ and CH_3C_6H_5~+) and the reactive pathway of nuclear alkylation of toluene with ethylene to para—ethyl toluene over Mg salt and phosphorus acid modified ZSM—5 zeolites have been studied by 1R and EPR methods.     

LINEAR ENTHALPY RELATIONSHIPS BETWEEN HEATS OF FORMATION OF COMPLEX COMPOUNDS AND HEATS OF PRO TONATION OF LIGANDS——COPPER(Ⅱ)-N-(PARA-SUBSTITUTED PHENYL) GLYCINES

The heats of protonation of N-(para-substituted phenyl) glycines (R—C_6H_4—NHCH_2COOH, R=CH_3O, CH_3, H, C1) and the heats of formation of these amino acids with copper(Ⅱ) have been determined calorimetrically at 25℃ in 30% (v/v) ethanol in the presence of 0.1M sodium perchlorate. The data obtained conform nicely to the equation △H_(ML)-Q-β△H_(HL) where △H_(ML) denotes the heats of formation of complex compounds, △H_(HL) denotes the heats of protonation of the ligands, and Q and β are constants.     

THE CRYSTAL STRUCTURE AND SPECTROSCOPIC PROPERTIES OF THE COMPLEXES FORMED BY TiCl_4 AND MgCl_2 WITH ESTERS——A RESEARCH ON THE STRUCTURE OF HIGHLY EFFICIENT CATALYSTS FOR POLYPROPYLENE

The complexes of TiCl_4, MgCl_2 and esters which are significant in industry have beenstudied by X-ray diffraction, IR and uv spectra. Their single crystal structures have also beendetermined. TiCl_4 and PhCOOEt can form two complexes, TiCl_4·L and TiCl_4·2L·MgGl_2, CH_3COOEtand H_2O form complex MgCl_2·2CH_3COOEt·2H_2O. All of them are molecular crystals. Theirspacial groups are C_(2h)~5-P2_1/c, C_(2h)~5-P2_1/n and C_(2h)~6-C_2/c respectively. From the XRD powderpattern, it has been ascertained that TiCl_4·L is formed in the process of the catalyst prepara-tion with milling-soaking method. Comparison between the IR spectra of the catalyst and Mgcomplex indicates that the coordinative bonds of the surface complex of the catalyst are verysimilar to that of the complex.     

STUDY ON THE REACTIVITY OF TRICARBONYL(PENTAMETHYL-DISILANYL)CYCLOPENTADIENYL MOLYBDENUM ANION

Some reactions of the title anion were studied.Bythese reactions six molybdenum complexes were prepared.On reac-tion with 1,3-dibromopropane the anion yielded the cyclic carbenecomplex(η-C_5H_4Si_2Me_5)MoBr(CO)_2CO(CH_2)_2CH_2.The crystal and mole-cular structures of (η-C_5H_4Si_2Me_5)MoBr(CO)_3 and 〔(η-C_5H_4Si_2Me_5)Mo-(CO)_3〕_2 Were determined by X-ray crystallography.     

TIME-RESOLVED IR STUDIES OF UV LASER FLASH PHOTOLYSIS OF W(CO)_6 IN C_6H_(12)-CCl_4 AND CCl_4 SOLUTION

Time-resolved IR absorption spectroscopy has been used to atudy the photochemistry of W(CO)_6 in cyclohexane, carbon tetrachloride, and the mixture of carbon tetrachloride and cyelohexane. The reastion of photolytically generated W(CO)_5. C_6H_(12) with CCl_4 was investigated. An intermediate with a lifetime of about 0.5ms, presumably attributed as W(GO)_5.CCl_4, was first observed.     

Cleavage of the Fe-Fe Bond of(Me_2SiSiMe_2)[η~5-C_5H_4Fe(CO)_2]_2 with Na/Hg and Molecular Structure of the Ring-Opened Complex

The reaction of the title cyclic complex(1) with sodium amal-gam in THF resulted in the expected cleavage of the Fe--Febond to afford bis-sodium salt (Me_2SiSiMe_2) [η~5-C_5H_4Fe(CO)_2Na]_2 (4). The latter was not isolated and was used di-rectly to react with MeI, PhCH_2Cl, CH_3C(O)Cl, PhC(O)Cl,Cy_3SnCl (Cy=cyclohexyl) or Ph_3SnCl to afford correspondingring-opened derivatives (Me_2SiSiMe_2) [η~5-C_5H_4Fe(CO)_2R]_2[5, R=Me; 6, R=PhCH_2; 7, R=CH_3C(O); 8, R=PhC     

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).