NMR AND INFRARED SPECTROSCOPIC STUDY ON THE INTERACTION OF RARE EARTH WITH L-METHIONIHE

Five solid complexes of rare earth with L-methionine have been prepared. The interaction of rare earth with the ligand has been studied by NMR and IR spectroscopy.     

A HREELS STUDY OF THE INTERACTION OF CYCLOHEXANONE AND PHENOL WITH Pt（111）SURFACE

ＡＨＲＥＥＬＳＳＴＵＤＹＯＦＴＨＥＩＮＴＥＲＡＣＴＩＯＮＯＦＣＹＣＬＯＨＥＸＡＮＯＮＥＡＮＤＰＨＥＮＯＬＷＩＴＨＰｔ（１１１）ＳＵＲＦＡＣＥ￥ＳｈｕＸｉａｎＺＨＵＡＮＧ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ，Ｕｎｉｖｅｒｓｉｔｙｏｆ...     

A STUDY OF THE INTERACTION AND FORMATION CONSTANTS OF NAPHTHALENE DERIVATIVES WITH CYCLODEXTRIN BY FLUORESCENCE AND CIRCULAR DICHROISM SPECTRA

The molecular recognition of the α,β-CD and 6~A,6~(C(D))-o,o′-(4,4′-diphenyloxide-disulfonyl)-β-CD to naphthalene derivatives was studied by fluorescence and circulardichroism spectra.The formation constants of the inclusion complexes were estimatedbased on the variation of fluorescent intensity and the modified Benesi-Hildebrand equa-tions.     

KINETIC STUDY ON THE EXTRACTION OF PALLADIUM(Ⅱ) WITH BIS(2-ETHYLHEXYL)SULFIDE

The effects of concentration, temperature, stirring rate and specific interfacial area onthe extraction of Pd (Ⅱ) with bis(2--ethylhexyl) sulfide (DEHS) were studied by the use of aconstant interracial area cell. The results support an interracial chemical reaction regime.     

A STUDY ON THE INTERACTION BETWEEN CH_3OH AND H_2CO MOLECULES IN TERMS OF THE PROPERTIES OF CHARGE DENSITY DISTRIBUTIONS

Two possible complexes formed by the interaction of CH_3OH and H_2CO,one hydrogen-bonded(Ⅰ)and one donor-acceptor complex(Ⅱ),have been reported in the previous paper.Based on theab initio 6-31G basis set calculations,the properties of the charge density for the complexeshave beenanalyzed using the theory of atoms in molecules.The nature of the complex formation has beendiscussed in terms of the properties of the charge density distributions.     

A FOURIER TRANSFORM INFRARED SPECTROSCOPIC STUDY OF THE REACTION BETWEEN POLY (VINYL PYRIDINE)S AND EPOXY COMPOUNDS

Chemical reactions between poly (vinyl pyridine)s and 1, 4-butanediol diglycidyl ether and other epoxy compounds were studied by Fourier transform infrared spectroscopy and other techniques. The epoxy group was found to react with the pyridine side group of poly (4-vinyl pyridine), forming crosslinked networks which contain cyclic amide structures. The reaction was also observed in the interracial region of poly(vinyl pyridine) and γ-glycidoxy propyl trimethoxysilane hydrolyzate (γ-GPS) coatings on PET fiber substrates. Poly(2-vinyi pyridine) does not show the same reaction.     

STUDY ON THE STRUCTURES OF COMPLEXES OF LANTHANIDE WITH BIDENTATE HETEROCYCLIC AMINE——THE STRUCTURE OF BIS[TRI(TRICHLOROACETATO)-1,10-PHENANTHROLINE-BTHANOL-GADOLINIUM]

<正> (GdC12H8N2(CCl3CO2)3C2H5OH)2,Mr=870.60,monoclinic,space group P21/n, a= 12.489(1), b= 18.5194(1),c=13.399(1)A,β=92.9(1)°,V=3095.2A3,Dc=1.868g/cm3 and Z=2. The structure was solved by Patterson and Fourier methods,and refined by full matrix least squares method to R=0.078 for 1619 observed reflections with I>3σ(I).The molecule of the complex is a dimer located at the crystallographic center and each Gd(Ⅲ) atom is eight-coordinated with the coordination polyhedron being a distorted square antiprism.     

CRYSTAL AND MOLECULAR STRUCTURE OF TETRACHLORO-BIS[BIS(2-ETHYLHEXYL)-SULFIDE]-PLATINUM(IV)

<正> C32H68Cl4S2Pt, Pt[(BEHS)2Cl4], Mr=853.9, space group P21/a, a =10.445(3), b=15.012(4), c = 13.506(5) A,β=101.43(3)°,V=2076(1) A3, Z=2, DC=1.37 g·cm-3, MoKa radiation, u= 39.3 cm-1, F(OOO) = 876 e, R = 0.053 for 1790 reflections. Pt(IV) is coordinated by four chloro atoms and two S atoms of BEHS, forming a somewhat distorted octahedron with Pt-S of 2.366 and Pt-Cl of 2.309A. The packing pattern of the long BEHS chain may allow the existence of conformational disorder.     

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.     

THE STUDY OF THE REACTION OF THE QUASI-AROMATIC COMPLEX [Ni(PnAO)-6H]~(?)WITH FORMALDEHYDE: KINETICS AND MECHANISM

The kinetics of the reaction of [Ni(PnAO)—6H]° with formaldehyde was studied in H_2O—CH_3OH solution under neutral condition and a complicated mechanism with three steps including competitive, consecutive and reverse reactions was proposed.     

A SPECTROPHOTOMETRIC STUDY OF THE COMPLEXATION EQUILIBRIUM OF IRON(Ⅱ)WITH 4-(2-THIAZOLYAZO)-RESORCINOL

4-(2-thiazolyazo)-resorcinol(TAR)can form complexes FeR,FeHR andFeR_2 according to numerical evaluation from experimental data of A and pH.Their cumulative stability constants(log B)are 11.48,15.32 and 17.30respectively.     

THE SYNTHESIS AND CHARACTERIZATION OF THE COORDINATION COMPOUNDS OF Pt(Ⅱ)AND Ir(Ⅲ)WITH 2-MERCAPTOPYRIDINE-1-OXIDE AND ITS METHYL DERIVATIVES

Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT~-,3Me-PT~-or 4Me-PT~-)are reported here.Four coordination compounds of the lattertwo ligands have never been reported before,while PT~-'s were synthesized withH_2PtCl_6 and(NH_4)_3IrCl_6 respectively,which were different from the methods ofDavidson et al.~1 and Sterinbrech~2.They were characterized by elemental analysis,UV,IR,~1HNMR and molar conductance.Their structural formulas have beendetermined,and the mechanism of synthetic reaction has been discussed.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF BIS [4,4,4-TRIFLUOR-1-(2-THIENYL) Butandion-1,3] COPPER (Ⅱ) WITH DIMETHYLFORMAMIDE, [Cu(TTA)_2(DMF)]

<正> [Cu(C8H4F3O2S)2(C3H7NO)], Mr = 579. 0, monoclinic, P21/c, a = 9. 4851(6), b = 26. 6574(6), c=9.2619(6) A ,β=96.08(3)°, V = 2328.7A3, Z=4, Dc=1. 65gcm-3, μ(MoKa) = 7. 2cm-1, F (000) = 1172, MoKa radiation, final R = 0. 074 and Rw = 0. 068 for 1841 reflections with I≥3σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by five oxygen atoms, one of which from DMF is in the axial position, to form a square pyramidal geometry. That the thenoyl groups in the ligands take the cis-form around the Cu(Ⅱ) atom is explained by the hydrogen bonding effect.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF BIS (1,1,1 TRIFLUORO 3-2-2'''' THENOYLACETONATO) COPPER (II) WITH PYRIDINE

<正> Mr=666.12, triclinic, Pl, a=8.868(1), b=9.719(2), c=10.861(1) A,α=58.23(1)°, β =64.06(1)° r =71.63(1)°; V =711.2 A3; 2=1, Dc=1.555 g.cm-3,for 3724 reflections with I≥ 3σ(I). In the title compound, the copper atomhas a distorted octahedral coordination with four Cu-O long bonds and twoCu-N short bonds. ,     

A NEW SYNTHETIC ROUTE TO α-ARYL PROPIONIC ACID AND A QUANTITA-TIVE STUDY OF THE PHOTO-S_(RN)1 REAC-TION OF ARYL HALIDES WITH CAN-BANION FROM ALKYL NITRILE

A new synthetic route leading to α-(2-(6-methoxynaphthy1))-propionic acid has ben developed. Successive one-step preparation of the appropriate α-aryl propionitrile from the aryl halides with propionitrile by photo-SRN1 procedure followed by hydrolysis gives the desired α-aryl propionic acid in excellent total yield. The photostimulated reaction of 2-bromonaph-thalene with acetonitrile or propionitrile in KNH2-NH3 solution to form the corresponding nucleophilic substitution product occurs with quantum yields considerably in excess of unit, while the pseudo-first-order rate constants of the photo-SRN1 are 30.9 and 47.0×10-5mol·s-1, respectively. Definite evidence to support the excitation of ground CTC and electron transfer from anion to ArX within the complex comes from the observation of the same φ>200 and φ>313 as well as MO calculation.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF BIS [4, 4, 4-TRIFLUORO-1-(2-THIENYL) BUTANEDIONE-1, 3] NICKEL (Ⅱ) WITH DIMETHYLSULFOXIDE, [Ni(TTA)_2(DMSO)]

<正> The title complex [Ni(TTA)2(DMSO)] (TTA = thenoyl trifluo-roacetone, DMSO=dimethyl sufloxide) belongs to triclinic, space group P1, parameters of crystal cell: a = 9.447(l), b = 10.505(1), c=11. 912(1)(?) , α=97. 42(1), β= 84. 00(1), γ = 102. 08(1)°, V = 1143. 3(?)3, Z = 2, Mr = 581. 22 [Ni (C8H4O2F3S)2(CH3)2SO)], Dc=1. 688g. cm-3, F(000) = 588, final R = 0. 065 and Rw = 0. 072 for 2873 reflections with I≥3σ(I). In the title complex the nickel atom has a square pyramidal geometry with four short Ni-O bonds and one long Ni -O (DMSO) bond.     

SYNTHESIS AND CRYSTAL STRUCTURE OF BIS (TETRAETHYLAMMONIUM) BIS[μ-(l,2-DITHIOETHELENE)-S,S']-BIS[l,2-DITHIOETHELENE-S,S']-DI-IRON(Ⅲ)

<正> INTRODUCTION. In our attempts of chemical simulation of the active center of nitrogenase we have been interested in the reaction system of various ferrous thiolates with thiomolybdatee. In previous papers, we have reported the syntheses of ferrous monodentothiolates and their reactions with tetrathiomolybdate. The possible structure type of ferrous thiolates when bidentothiols are used inspired our interest in this work.     

A THEORETICAL STUDY ON THE STRUCTURES AND ENERGIES OF DIMER AND TRIMER OF DELTIC ACID （2，3—DIHYDROXYCYCLOPROPENE—1—ONE）

<正> The structures of deltic acid,its diner, and its trimer have been studied by semiempirical chemical method AMI.The stabilization energies of dinerization and trinerization are 32 and 65 kJ/mol- aspectively. The length of hydrogen-bond R(O...H-0) in diner is 3.04A,while the sane bond is slightly longer in trimer(R=3.06A).     

SYNTHESIS AND CRYSTAL STRUCTURE OF A HETERODINUCLEAR COMPLEX OF PALLADIUM SILVER WITH BRIDGING BIS-( DIPHENYLPHOSPHINO ) METHANE [ 1 ]

<正> A heterodinuclear complex, trans- dicyano- palladium (Ⅱ)- bis [β- bis (diphenylphosphino)methane]-nitritosilver(Ⅰ),has been prepared by treatment of trans-(NC)2Pd(dppm)2 with AgNO2 and characterized by elementary analysis, ir, nmr, and X-ray crystal structure determination. AgPdC52H44N3O2P4,Mr= 1081. 12,monoclinic,space group P21/c,a=14. 745(7),b= 19. 208(7),c= 17. 486(6) A ,β=94. 99°(2) ,and Z = 4. The final R=0. 032 for 8673 unique reflections. In the molecule,the Pd -Ag distance is 3. 205 A. The palladium moiety has an approximately square planar geometry, and the silver moiety has a severely distorted tetrahedral geometry.     

SYNTHESES AND STRUCTURAL STUDIES OF Mo-Fe-S-CLUSTER COMPOUNDS Ⅶ.SPECTROSCOPIC STUDY OF THE [MoFe_3S_4] CUBANE UNIT IN (Bt_4N)4(Mo_2Fe Sa(SR)_12] AND RELATED COMPOUNDS

<正> INTRODUCTION. In the study of nitrogenases, scientists have proposed many models for the active center of MoFe protein and for FeMoco. All of them contain a basic structural unit [FeS_2M] (M=Fe or Mo). We have reported some structural regularities in a series of linear Mo-Fe-S compounds. In order to investigate the electron distribution and the synergism of metal atoms within a Mo-Fe-S cluster with [MoFe_3S_4] cubane unit, we have synthe