EFFECTS OF CONFORMATION OF POLYMER LIGANDS IN COPPER(Ⅱ) COMPLEXES ON CATALYLIC ACTIVITIES AND MECHANISM OF OXIDATIVE COUPLING OF β-NAPHTHOL

Copper(Ⅱ) complexes of sericin, chitosan, 6-and 2-aminodeoxystarch were used as catalysts in oxidative coupling of β-naphthol, the effects of conformation of the polymer ligands in these complexes on activities of the catalysts and mechanisms of the reaction were studied. It was found that if the catalysts react with the substrate by mechanism similar to the enzymic catalysis they must be composed of polymer ligands with highly coiled, especially with densely helicoidal, conformations. While catalysts composed of loosely coiled or helicoidal hgands react with the substrate through molecular collision and have relatively lower activities only. Under nitrogen, catalysts from sericin and chitosam reacting with β-naphthol give optically active β-binaphthol, rotating polarized light to right, but the stereoselectivities are rather low.     

REACTION OF BIS(β-ALANINATO)COPPER(II) WITH FORMALDEHYDE: X-RAY CRYSTAL STRUCTURE OF AQUABIS(N,N-DIMETHYL-β-ALANINATO)COPPER(II) HEXAHYDRATE

Abstract

The reaction of bis(β-alaninato)copper(II) with formaldehyde results in the formation of blue crystals of aquabis(N,N-dimethyl-β-alaninato)copper(II) hexahydrate, [Cu(C₅H₁₀NO₂)₂(OH₂)].6H₂O which crystallize in the monoclinic space group C2/c with unit cell dimensions a = 20.799(2), b = 8.112(1), c = 23.639(1)Å, β = 96.50(1)° and Z = 8. The structure has been refined to final R = 0.047 and R_w = 0.053 for 1690 reflections with I ≥ 2.55σ(I).     

REPLACED SITE OF Eu~(2+) ION IN THE COMPLEX FLUORIDES WITH THE PEROVSKITE CRYSTAL STRUCTURE

The replaced site of Eu~(2+) ion is dependent on the electronegativitydifference of the cations in complex fluorides.In the mixed fluorideKMgF_3:Eu~(2+),Eu~(2+) ion occupies K~+ site,its emission spectrum is a sharpline and its valence-state is stable.     

CRYSTAL STRUCTURE OF THE COPPER（II） COMPLEX OF NEW MACROCYCLIC DIOXOTETRAAMINE LIGAND FUNCTIONALIZED WITH 8－METHYL QUINOLINE PENDANT

ＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＯＦＴＨＥＣＯＰＰＥＲ（ＩＩ）ＣＯＭＰＬＥＸＯＦＮＥＷＭＡＣＲＯＣＹＣＬＩＣＤＩＯＸＯＴＥＴＲＡＡＭＩＮＥＬＩＧＡＮＤＦＵＮＣＴＩＯＮＡＬＩＺＥＤＷＩＴＨ８－ＭＥＴＨＹＬＱＵＩＮＯＬＩＮＥＰＥＮＤＡＮＴ￥ＸｉａｎＨｅＢ...     

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.     

ELECTRONIC STRUCTURES AND BONDING PROPERTIES OF MIXED LIGAND COPPER(II) COMPLEXES OF 2-(2-PYRIDYLETHYL)PICOLYLAMINE AND DIPICOLYLAMINE. MOLECULAR STRUCTURES OF (2,2′-BIPYRIDINE)[2-(2-PYRIDYLETHYL)PICOLYLAMINE]COPPER(II) PERCHLORATE AND (DIPICOLYLAMINE)(1,10-PHENANTHROLINE)COPPER(II) PERCHLORATE

Abstract

Mixed ligand copper(II) complexes of 2-(2-pyridylethyl)picolylamine (pepica) of [Cu(pepica)(pi-colinato)](ClO₄)(H₂O) and the [Cu(pepica)(L)](ClO₄)₂ type, where L stands for 2,2′-bipyridine (bipy), 1,10-phenanthroline, neocuproine, and ethylenediamine, and dipicolylamine(dipica) of the [Cu(dipica)(L)](ClO₄)₂(H₂O) _n type, where L for 2,2′-bipyridine (n = 0), 1,10-phenanthroline (phen, n = 0), and neocuproine (n = 1), have been synthesized and characterized by elemental analyses, and IR, electronic and EPR spectroscopic measurements. The molecular structures of [Cu(pepica)(bipy)](ClO₄)₂ (1) and [Cu(dipica)(phen)](ClO₄)₂ (2) have been determined using three dimensional X-ray diffraction data. Complex 1 consists of discrete distorted square pyramidal [Cu(pepica)(bipy)] cations, with a meridional pepica ligand and one of the pyridine rings of the bipy ligand forming a basal plane. The other pyridine nucleus of the bipy is bound at the apex having an elongated bond distance of 2.255 Å and tilted off the normal z axis by ～15°. Complex 2 comprises discrete distorted trigonal bipyramidal [Cu(dipica)(phen)] cations, with the two pyridine nuclei of the dipica ligand and one of the pyridine rings of the phen forming an equatorial trigonal plane and the remaining pyridine ring of the phen and the amine nitrogen of the dipica on the axial sites. The trigonal bipyramidal cation, distorted toward a square pyramidal structure, has an enlarged equatorial N(py)–Cu–N(py) angle of 132.4° and an elongated equatorial Cu–N(phen) bond of 2.156 Å. All of the complexes exhibit axial type EPR spectra. Gaussian resolved d-d spectra for these complexes, except the dipica-bipy and dipicaphen ones, yield an orbital sequence of d_x ²- _y ² ≥ d_z ² > d_xy > d_yz ～d_xz . The bonding properties of the tridentate and the bidentate ligands are elucidated.     

INFLUENCES OF LIGANDS ON THE HOMOGENEOUS HYDROFORMYLATION OF ALKENE(I)-TRI-(3,4-DIMETHYLPHENYL)PHOSPHITE AS A LIGAND

In this paper we describe the effects of tri(3, 4-dimethylphenyl)phosphite[(3,4-(CH_3)_2C_6H_3O)_3P]or triphenylphosphine(PPh_3)used as ligand in the homogeneoushydroformylation of alkene using dicarbonyl acetylacetone rhodium as the parent catalyst.The reaction kineties has been investigated.It was found that tri(3,4-dimethylphenyl)-phosphite has greater activity and better selcctivity than PPh_3 for hydroformylation ofheptene-1.The results are discussed in terms of eiectronic and stereochemical effects.     

PREPARATION AND CRYSTAL STRUCTURE OF A HETEROBINUC- LEAR COPPER (Ⅱ)-ZINC(Ⅱ) COMPLEX WITH μ-OXAMIDO LIGAND

<正> The complex [Cu(oxap)Zn(phen)2](ClO4)2·H2O·CH3CH2OCH2-CH3(Mr = 980. 61) (oxap = N,N'-bis(2-aminopropyl) oxamido C2O2 (NCH2CH(CH3) NH2)2, phen = 1, 10-phenanthroline) crystallizes in the monoclinic space group P21/n with a=13. 076(4),b=23. 039(7) ,c= 14. 375(3) A,β=98. 11(2)°,V = 4287. 2A3, Z = 4,DX = 1. 541g/cm3,μ=12. 80cm-1 and F(000) = 2020. The final refinement converged with R=0. 067 for 3173 observed independent reflections. The copper(Ⅱ) ion is in an almost planar tetragonal environment while the zinc(Ⅱ) ion is in a distorted octahedron. The Cu....Zn distance is 5. 265A.     

SYNTHESIS AND CRYSTAL STRUCTURE OF THE LANTHANIDE COMPLEX WITH MIXED LIGANDS [Pr (CH_3COO)_2(NO_3)(Phen)]_2

<正> [Pr(CH3COO)2(NO3)(Phen)]2, Mr = 1002. 41. The crystal is monoclinic, space group I2/m, with a = 11. 725(5), b = 12. 269(5), c=12. 732(4) A, V = 1792(2)A3,β=101. 88(0)°. Z = 2, Dc=1. 86g/cm3,μ(MoKa) = 27. 5cm-1, F (000) = 984. The structure was solved by Patterson method and Fourier syntheses, and refined by full matrix least-squares method to R = 0. 033 for 1660 observed reflections with I>3σ(I). The molecule of the complex is a dimer and each praseodymium atom is eight-coordinated in a distorted square antiprism geometry.     

STUDIES ON THE CRYSTAL STRUCTURE OF Al-(D-TRYPTOPHAN) INSULIN

We have determined the crystal structure of Al-(D-Trp) insulin and discovered that it belongs to the trigonal system with space group R3. The parameters of the unit cell are a=b=78.6, c=50.0. A set of data for half a sphere reciprocal space to a spacing of 2.2 were collected. The model was adjusted and refined by using a step-by-step approach and a stereochemically-restrained least squares program, assisted by manual revision based on the difference Fourier maps, to a final R-factor of 0.218. The main and side chains of both Al-D-Trp residues in the asymmetric unit are well ordered. The packing of Al-(D-Trp) insulin in the unit cell, the conformational differences with other insulin structures and its structure and function relationship bave also been discussed.     

THE CRYSTAL,MOLECULAR STRUCTURE AND LIGAND BONDING IN TETRAKIS (N,N′-DIMETHYLTHIOUREA) NICKEL (II) BROMIDE DIHYDRATE

Abstract

The crystal structure of tetrakis(N,N′-dimethylthiourea)nickel(II) bromide dihydrate has been determined by three-dimensional x-ray diffraction from 1916 counter-data reflections collected at room temperature.

The structure consists of Ni[SC(NH)₂(CH₃)₂]²⁺ ₄ molecular ions, Br^? ions and waters of hydration. The nickel is located on a center of symmetry and is coordinated to four sulfur atoms in a square planar configuration. The waters of hydration and the bromide ions are involved in hydrogen bonding to the N,N′-dimethylthiourea (dmtu) groups. The orientation of the dmtu groups is such that two bond through the sulfur sp² orbital and the others bond through the π-orbitals of the dmtu group. The Ni-S distances are 2.204 ± 0.002 Å and 2.230 ± 0.002 Å, and the Ni-S-C angles are 106.2 ± 0.2Å and 110.3 ± 0.3°. The dmtu groups are planar except for methyl hydrogens.

The crystals are monoclinic, P2₁/a with a = 13.424 ± 0.002 Å, b = 12.321 ± 0.005 Å, c = 8.460 ± 0.008 Å β = 107.07 ± 0.05°, ρ₀ = 1.67 g cm^?3, ρ_c = 1.66 g cm^?3 and Z = 2. The structure was refined by full-matrix least-squares to a conventional R of 0.0466.     

THE PREPARATION AND CHARACTERISATION OF SALTS OF cis-BIS(2,2′-BIPYRIDINE)-CHLORO(DIMETHYLSULFOXIDE)-RUTHENIUM(II) AND THE CRYSTAL STRUCTURE OF THE PERCHLORATE DIHYDRATE. PRECURSORS FOR DNA-BINDING RUTHENIUM(II) COMPLEXES

Abstract

The preparation and characterisation of salts of the complex cation cis-bis(2,2′-bipyridine)-chloro(dimethylsulfoxide-S)ruthenium(IIII), [Ru(bpy)₂Cl(dmso)]⁺, is reported. The complex was prepared by the reaction of 2,2′-bipyridine with RuCl₃ · 3H₂O in dimethylsulfoxide. The value of this complex arises from its ability to react with suitable bidentate ligands particularly those that could act as DNA intercalators. The structure of [Ru(bpy)₂Cl(dmso)][ClO₄] · 2H₂O has been determined by single crystal X-ray diffraction. The complex crystallises in space group PI with a = 8.205(3), b = 10.448(4), c = 16.769(6) Å; α = 78.99(3)°, γ = 77.47(3)°, γ = 72.20(3)°, Z=2. The structure was refined by least-squares methods using 4070 observed reflections with 196 variable parameters (final R = 0.039).     

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. ,     

COMPLEXES OF 4,5-DIAZAFLUORENE AND 9,9′-BIS(4,5-DIAZAFLUORENYL) WITH NICKEL(II), COPPER(II) AND ZINC(II)

Abstract

Complexes having the compositions [LMCl₂], [L₂MCl₂], [L₂Cu][PF₆], [L′MCl₂] and [L′(MCl₂)₂] of 4,5-diazafluorene, L, and 9,9′-bis(4,5-diazafluorenyl), L′, have been prepared from MCl₂ (M = Ni, Cu, Zn) and characterised. Steric strain or the bite angle of the pro-ligand has no recognisable effect on its coordination chemistry with smaller 3d-metals.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF Ni(TAAB)(BF_4)_2WITH PYRIDINE

The crystal structure of [Ni(TAAB)(py)_2](BF_4)_2,where TAAB is thetetradentate macrocyclic ligand tetrabenzo[b,f,j,n] [1,5,9,13]tetraazacyclohexadecine,has been determined from X-ray diffraction analysis.The crys.tai beiongs to monoclinic,space group P2_1/n with cell parameters     

CRYSTAL STRUCTURE OF ADDUCT OF BIS(O,O''''-DIBUTYLDITHIOPHOSPHATO)-NICKEL (II) WITH BIPYRIDYL

<正> Ni[(C8H9O)2PS2]2 bipy, Mr=697.57, triclinic, Ci-Pl, a=9.469(1)A, b=14.638(3)A, c=14.637(2)A, α=69.64(1)° , β=71.16(1)°, r=89.99(1)°, V= 1785.6A3, Z=2, Dc=1.297g.cm-3, Mo kα radiation, λ=0.71073A, F(000)=736e, R=0.081 for 4986 independent reflections. Ni(II) is coordinated by four sulfur atoms and two nitrogen atoms to form a distorted octahedron. The angles between each two among planes N2Ni, NiS(11)S(12) and NiS(21)S(22) are nearly 90°.     

THE SYNTHESES OF POLYQUINOLINES WITH 2,2''''-PYRIDYLQUINOLINE AND 2,6-DIQUINOLYLPYRIDINE AS LIGAND AND THEIR APPLICATIONS IN SOME CATALYTIC REACTIONS

The polyquinolines with 2,2'-pyridylquinoline as bidentate and 2,6-diquinolylpyridine as tridentate ligand have been prepared from 4,4-dlamino- 3,3'-dibenzoyldiphenyl ether, 4,4'-diacetyldiphenyl ether and 1,4-bis (2-acetylpyridyl-6-oxy) benzene, 2,6-diacetylpyridine, respectively. These polyquinoline-supported ligands have been used in hydrogenation and hydroformylation of olefins with some transition metal complexes.     

AXIAL COORDINATION IN COBALT(II) COMPLEXES OF TWO SYNTHETIC MACROCYCLIC LIGANDS CONTAINING THE BIDENTATE α-DIIMINE GROUP

Abstract

In order to elucidate the nature of axial coordination in synthetic macrocyclic complexes of cobalt(II), we have synthesized two new series of such complexes, containing the macrocycles Me₄ [14] 1,3,8,10-tetraeneN₄ and Me₂ [14] 1,3-dieneN₄, by direct isolation of the Co(II) complexes from the condensation reaction mixtures. The complexes are formally five-coordinate in the solid state, but exhibit a tendency toward six-coordination in the presence of potential axial ligands, as demonstrated by electronic spectral and electron paramagnetic resonance studies. The Co(tetraeneN₄)⁺² and Co(dieneN₄)⁺² species are compared with the previously studied Co(Me₆ [14] 4, 11-dieneN₄)⁺² moiety with respect to axial coordination. It is concluded that the presence of methyl substituents on the six-membered chelate rings of the latter complex have a marked effect on its tendency to coordinate axial ligands.     

SYNTHESIS AND STRUCTURE OF Cu(Ⅱ)COMPLEXES BY OXIDATIVE ADDITION OF DIBENZOYL PEROXIDE ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metallic copperpowder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol andtetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1)and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methodsand Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7),b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4),b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055,Rw=0.062.     

SYNTHESES OF TUNGSTEN COMPLEXES WITH o-MERCAP-TOPHENOL.CRYSTAL STRUCTURE OF (Ph_4P)[WO(OMe)(mp)_2]

<正> Reaction of WCl6, mpH2 o-mercaptophenol) and MeONa in the presence of Ph4PBr gave complexes (Ph4P)[W(mp)3] (1) and (Ph4P) CWO(OMe) (mp)2] (2). Crystal data complex (2), C37H31O4PS2W, Mr = 818. 61, monoclinic, space group P2/a, a=26. 555(3), b=9. 634(1), c=13. 523(7) A. β=94. 68 (2)°, V=3448. 1 A3. A=1. 58 g/cm3, Z = 4. λ(MoKα)=0. 71073 A , μ= 36. 2 cm-1, F(000) = 1624, T=296K, final R(Rw) = 0. 068(0. 070) for 3929 observed reflections. The WO4S2 core is arranged in a distorted octahedral geometry.