BINUCLBAB COPPER(Ⅱ) COMPLEXES OF SOME PLANT GROWTH-STIMULATING SUBSTANCES.Ⅰ.SYNTHESIS AND STRUCTURE OF BIS(N,N-DIMETHYLFORMAMIDE)-TETHAKIS(μ-INDOLYL-3-ACETOXY) DICOPPER(Ⅱ)

<正> The structure of the title compound (Mr = 969.99) has been determined by X-ray analysis. The crystals are monoclinic, space group P21/n with a =14.746(2),b= 10.782(7), c = 15.531(3) A,β=113.74(2)°,Z=2,and DC=1.425g·cm-3. The final refinement converged with R = 0.067 and Hw=0.080 for 4491 observed reflections with I>3σ(I).     

SYNTHESIS, STRUCTURE AND MAGNETISM OF μ-OXAMIDO BINUCLEAR COPPER(Ⅱ) COMPLEXES

Two new binuclear copper(Ⅱ) complexes, [Cu(oxpn)CuL](ClO_4)_2, have been synthesizedand characterized, where oxpn is N,N' bis(3-aminopropyl)oxamido and L is 1,10-phenan-throline (phen) or 5-nitro-1,10-phenanthroline (NO_2-phen). The crystal structure and vari-able-temperature magnetic susceptibility (4- 300 K) of the Complex (L=phen) have beendetermined. Crystal data: orthorhombic system, space group Pnma, with a = 10.433(1), b11.458(2), c = 21.999(2)A, z = 4. Every copper(Ⅱ) ion is in a square pyramidal environment.The two copper(Ⅱ) ions are linked by μ-oxamido bridge and the separation of them is 5.208A. The singlet-triplet energy gap J was found equal to -452.92cm~(-1), indicating that astrongantiferromagnetic spin-exchange interaction operates between the copper(Ⅱ) ions.     

SYNTHESIS AND MAGNETISM OF BINUCLEAR COPPER(Ⅱ) COMPLEXES CONTAINING SALUCYLAMIDATOCUPRATE(Ⅱ)

New binuclear copper(Ⅱ) complexes, [Cu(samen)Cu(NO_2-phen)]·H_2O and [Cu(sampn)-Cu(NO_2-phen)]·2H_2O have been synthesized, where samen~(4-), sampn~(4-) and NO_2-phen denote N, N′-ethylenedisalicylamidate anion, N, N′-1, 2-propanedisalicylamidate anion and 5-nitro-1, 10-phenanthroline respectively. 3ased on IR, elemental analyses and electronic spectra, the complexes are proposed to have a phenoxy-bridged structure and to consist of the Cu(Ⅱ)ion in distorted planar environment. The complexes have been characterized with varlable-temperature magnetic susceptibility (4—300 K) and the observed data were fit to those from a modified Bleaney-Bowers equation by least-squares method, giving the exchange integral J=-63.0 cm~(-1) (samen) and J=-46.5cm~(-1) (sampn). This indicates the existence of antiferromagnetic spin exchange interaction among the metal ions.     

SELENOETHER COMPLEXES OF COPPER(II) ‐ SYNTHESIS,SPECTROSCOPY AND STRUCTURES

Abstract

The red-brown copper(II) diselenoether complexes, [Cu (L-L)₂][BF₄]₂ (L-L = MeSeCH₂CH₂SeMe, MeSeCH₂CH₂CH₂SeMe or PhSeCH₂CH₂SePh) have been prepared from copper(II) fluoroborate and the ligands in anhydrous dichloromethane. Some new dithioether analogues are also described. The reaction of MeSeCH₂CH₂SeMe and copper(II) fluoroborate in ethanol led to an unstable dark green substance which appeared to contain both copper(I) and copper(II) and was formulated [Cu(MeSeCH₂CH₂SeMe)₂] [BF₄]_x. The complexes were characterised by analysis, UV-visible and e.p.r. spectroscopy, and magnetic measurements, and cyclic voltammetry has been used to probe the Cu (II)/Cu(I) redox couples. The complexes are too unstable in solution to obtain crystals for an X-ray study, but structural data has been obtained for both the Cu(II) and Cu(I) complexes by copper K-edge EXAFS studies. Ditelluroethers reduce copper(II) salts to copper(I) complexes.     

CALORIMETRIC STUDY OF THERMOCHROMIC COMPLEXES. 2. HEAT CAPACITY AND PHASE TRANSITION OF BIS(N,N‐DIETHYLETHYLENEDIAMINE)COPPER(II) PERCHLORATE

Abstract

The thermochromic phase transition of bis(N,N-diethylethylenediamine) copper(II) perchlorate has been studied by adiabatic calorimetry in the 12–359 K temperature range. A large heat capacity anomaly was observed at 317.64 K with a long heat-capacity tail extending down to ～200 K. The enthalpy and entropy of the phase transition were found to be δ_trs H = 17.43 kJ mol^?1 and δ_trs S = 55.21 J K^?1 mol^?1, respectively. Together with a calorimetric study of a homologous thermochromic complex, bis(N,N-diethylethylenediamine)copper(II) tetrafluoroborate (J. Phys. Chem. Solids, 55, 99 (1994)), the nature of the present thermochromic phase transition is well described by a puckering motion of the copper-ligand chelate rings and a change in the ligand-field strength estimated on the basis of the angular overlap model. The correlation between structures, electronic spectra and thermal properties is discussed.     

SYNTHESIS AND MAGNETIC PROPERTY OF CARBOXYL BRIDGING DICOPPER(Ⅱ) COMPLEXES

Two new dicopper(Ⅱ) complexes with two carboxyl bridgings in one molecule[Cu(dm-phen)(HCOO)]_2(NO_3)_2 3H_2O(1). [Cu(ds-phen)(CH_3COO)]_2 (NO_3)_2 3H_2O(2). one dicopper(Ⅱ) complex with one carboxyl bridging and one hydroxo bridging in one molecule [Cu_2(OH)(C_2H_5COO)(ds-phen)_2]. (NO_3)_2 H_2O(3) and one cononuclear Cu(Ⅱ) complex [Cu(de-phen)(CF_3COO)](NO_3).H_2O(4)(dm-phen= 2,9-dimethyl-1,10-phenanthrolin)were prepared and characterized. The effective magnetic moment, u elf, was measured and their magnetic properties were discussed. The coordination modes of carboxyl moieties in all the title complexes were proposed.     

A NOVEL SYNTHETIC METHOD AND STRUCTURE OF TETRAKIS(BENZOATE)BIS(TRIPHENYLPHOSPHINE OXIDE)DICOPPER(II).OXIDATIVE ADDITION OF DIBENZOYL ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metalliccopper with triphenylphosphine in a mixed solvent(acetone,dichloromethaneand trichloromethane),and affords the binuclear copper complex(Cu(C_6H_5COO)_2(OPPh_3))_2.Crystals are monoclinic,space group A_2/a,withcell parameters,a=24.337(3),b=10.566(1),c=21.579(2),β= 93.18(1)°,V=5540(1)~3,Z=4,R=0.042,and Rw=0.044 for 5872 observed reflections.Each copper ion is coordinated by four bridging benzoato ligands and onetriphenylphosphine oxide group to form binuclear complexes.     

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.     

STRUCTURES OF COPPER(I) AND ZINC(II) COMPLEXES WITH N,N′-BIS(2-PYRIDINYL)THIOUREA (BPT)

Abstract

Copper(I) and zinc(II) complexes with N,N′-bis(2-pyridinyl)thiourea (BPT), [Cu(BPT)₂]ClO₄ (1) and [Zn(BPT)₂](ClO₄)₂ (2) were synthesized by reaction of M(ClO₄)₂ (M = Cu, Zn) with BPT in methanol solution. The crystal structures of complexes (1) and (2) were characterized by X-ray diffraction: (1) is triclinic, space group P, with a = 10.162(2), b=14.483(6), c = 9.496(2) Å, α = 105.80(2)°, β = 106.94(2)°, γ = 82.71(3)°, V = 1284.4(7) ų, Z = 2, and final R = 0.047, R _w = 0.061; (2) is monoclinic, space group C2/c, with a = 15.15(1), b = 6.299(3), c = 30.16(1)Å, β = 93.49(7)°, V = 2872(2)ų, Z=4, and final R = 0.049, R_w = 0.070. Both of the complexes exhibit novel structures. Two N atoms and two S atoms from two BPT groups coordinate to one M atom. The M atom shows distorted tetrahedral geometry. IR spectra and ther-moanalyses of BPT and its complexes (1) and (2) are briefly discussed.     

CRYSTAL STRUCTURES OF COPPER (Ⅱ) AND COBALT (Ⅲ) COM- PLEXES OF o-HYDROXYBENZYLGLYCINATE (HBG)

<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of     

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.     

PREPARATION, CHARACTERIZATION AND ELECTROCHEMISTRY OF BINUCLEAR COPPER(I) COMPLEXES Cu_2(dppm)Cl_2 AND Cu_2(dppe)Cl_2

Two binuclear copper(I) complexes with novel structures and novel bonding,Cu_2(Ph_2PCH_2PPh_2)Cl_2 (Ph_2PCH_2PPh_2=dppm) and Cu_2(Ph_2P-CH_2CH_2PPh_2)Cl_2 (Ph_2PCH_2CH_2PPh_2=dppe), were prepared and characterized through elemental analyses, ICP, IR(4000-200 cm~(-1), CsI disc.), ~(31)P-NMR spectra. Their electronic conductivities, oxidation and reduction potentials were measured. Preliminary studies show that both of the two complexes have chlorobridging and phosphorus-bridging structures.     

A NOVEL BINUCLEAR COPPER(II) COMPLEX: BIS[1,10-PHENANTHROLINE-N,N′-MALEATO- O,O′-COPPER(II)] DIMETHANOL TETRAHYDRATE

Abstract

A novel binuclear Cu(II) complex, [Cu₂(mal)₂(phen)₂]. 4H₂O. 2MeOH (phen= 1,10-phenanthroline, mal = maleato dianion), has been synthesized and characterized by elemental analysis, IR spectroscopy, solid-state ESR analysis and X-ray single crystal study. The complex consists of [Cu(mal)(phen)] subunits with two water and one methanol solvate molecules. The subunits show a distorted planar arrangement, existing in centrosymmetrically related pairs in the crystal packing. They have a distorted four-coordinate square-planar arrangement of N and O atoms about the central Cu atom; pairs of these [Cu(mal)(phen)] subunits form dimers by interaction of the fifth position on each Cu center with an O atom of a maleato ligand of the associated subunit with a Cu-Cu distance of 3.3425(9) å. The coordination around each Cu atom is best described as distorted square-pyramidal. The lattice water and methanol molecules are also confirmed by the TG study and IR spectra. The X-band solid-state ESR spectrum at room temperature exhibits an anisotropic feature with g′ = 2.24, g′ = 2.06.     

ESR SPECTRA STUDY OF COPPER(Ⅱ) COORDINATION COMPLEXES OF PYRIDI

The ESR spectra of powdered samples of Cu(Ⅱ) complexes with pyridine and its sixhomologues and pyrrol, aniline, as well as their solutions are measured at 77K in this paper.The electronic levels of these complexes are calculated from the ESR spectral parameters.It is found that the non-pyridine ligands of complexes which can be substituted by pyridinemolecules of solvent in solution of pyridine/chloroform form Py_4Cu~(2 ). A molecular configura-tion is proposed. for Py_4Cu~(2 ) in solution. It is shown that the treatment with D_(2h) symmetryinstead of D_(4h) symmetry leads to a more satisfactory explanation of the ESR spectra.     

CRYSTAL STRUCTURE OF BIS(μ-SULFIDO)-BIS[OXO-DIETHYL-DITHIOCARBAMATO-MOLYBDENUM(V)]

<正> INTRODUCTION. Reaction of MoCl_3·3H_2O with dithio-carbamate to synthesize dinuclear or trinuclear molybdenum complexes is an interesting topic. We have obtained sulfido-bridged molybdenum(V) complex Mo_2(μ-S)_2O_2(S_2CNEt_2)_2 by reacting MoCl_3·3H_2O with NadtcEt_2 in MeOH solvent. The molecular structure of the title compound was characterized by, X-ray structure determination. We report the result of the structure determination in this paper.     

SYNTHESIS, SPECTRA AND ELECTROCHEMICAL PROPERTIES OF OXYGEN ADDUCTS OF TETRAKIS(2-ANILINOPYRIDINATO) DIRHODIUM COMPLEXES

Two oxygen adducts of different geometric isomers of the tetrakis(μ-2-anilinopyridinato) dirhodium unit, Rh_2(ap)_4~+, have been synthesized and characterized. Rh_2(ap)_4O_2(4,0) is the oxygen adduct 1 of 4, 0 isomer; and Rh_2(ap)_4O_2(2, 2) is the oxygen adduct 2 of 2, 2 isomer. The ESR spectra of both oxygen adducts show that there is a characteristic signal of a superoxide ion, g=2.03. The 4, 0 isomer with different axial ligands gives the order of A_Ⅱ values; O_2~-≈ClO_4~-相似文献   

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.     

STUDY ON BINUCLEAR COPPER(I)COMPLEXES III.SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMISTRY OF DICHLORO-TRIS(4-VINYLPYRIDINE)-DICOPPER(I)COMPLEX

Recent years,many novel complexes have been prepared by usinghetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridinewhich has two different coordinating sites have not been reported,and only a fewcomplexes of Cu(I)have been published~(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Clwas prepared and characterized by elemental analyses,ICP,IR,and electronicspectra.Its conductivity,oxidation potential and reduction potential weremeasured.     

SYNTHESES OF POLYMER-BOUND RHODIUM COMPLEXES AND THEIR APPLICATION AS CATALYSTS FOR THE HYDROFORMYLATION OF DIISOBUTYLENE (Ⅱ)

Five kinds of polymer-anchored aminophosphine-rhodium complexes were synthesizedby ionic and covalent bonding methods. These anehored rhodium complexes synthesizedpossess good catalytic activity and aldehyde-formation selectivity in the hydroformylationof diisobutylene. The complexes anchored via covalent bonds on polymers showedexcellent reproducibility on recycling. After reaction, it indicated that the loss of rhodiumof the catalysts was very small as shown by analysis.     

PREPARATION, PROPERTIES, AND MOLECULAR STRUCTURE OF trans-DICYANO BIS[BIS(DIPHENYLPHOSPHINO) METHANE]PALLADIUM (Ⅱ)

<正> The crystal structure of the title compound has been determined. PdC52H44N2P4, Mr = 927. 2, monoclinic, space group P21 /n, a =12. 102(2), b = 9.997(2), c=20. 254(5)(?),β=93. 80(2)°, V = 2445. 0(?)3, Z = 2, R =0. 075 and Rw = 0. 095 for 3535 observed reflections (I>3σ(I)), The palladium atom is located on the symmetric center and adopts a square planar coordination surroundings with two biphosphine ligands and two cyanide groups. The molecular structure in crystals is different from that in solution in which the molecule is very fluxional, probably due to the rapid alteration in coordination sites between the coordinated and uncoordinated phosphorus atoms of the biphosphine ligands. Their properties are also reported.