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1.
EPR studies have been carried out on a series of copper(IIcomplexes with the general formula CuL(NCS)xY2-x[L = N,N,N',N″,N″-pentamethyldiethylenetriamine (Me5den); x = 1 or 2; and Y = ClO4, NO3 or B?4], dissolved in different solvents. These studies have revealed that the symmetry around copper(II) in [Cu(Me5den)(NCS)2] and [Cu(Me5,den)-NCS]NO3 is not trigonal-bipyramidal as predicted by IR, conductivity and optical data. The 4s contribution to the ground state is found to influence the isotropic contact term and bond parameters. The hyperfine line-widths observed for the copper(II) ion in solutions of these complexes dissolved in pyridine at room temperature are explained using the theory of Wilson and Kivelson. The isotropic spin—rotational relaxation contribution to the residual line-width is found to be smaller for all the complexes when they are dissolved in pyridine. 相似文献
2.
This paper presents EPR, and optical absorption studies on [Cu(tren)NCS]SCN and [Cu(Me6tren)NCS]SCN in solutions. Expressions derived by Barbucci and Bencini are evaluated. It is shown that the molecular motion of the complexes is anisotropic and nondiffusional. 相似文献
3.
Summary Reaction of 1,4,8, 12-tetra-azacyclopentadecance ([15])-aneN4) with an excess of acrylonitrile gives theN-tetracyanoethylated ligand (L). Several new complexes of this ligand with nickel(II), copper(II) and zinc(II) have been prepared and characterised. The complexes can be formulated [NiL]n(ClO4)2n, [ML](ClO4)2 (M=CuII and ZnII), [NiL(NCS)2], [NiLCl2], [CuL](NO3)2 and [NiL]n(NO3)2n·2H2O. Spectral, magnetic and conductivity data are reported and possible structures are considered. 相似文献
4.
《Journal of organometallic chemistry》2005,690(24-25):5989-6000
The β-diketiminato Cu(I) arene adduct {[Me3NN]Cu}2(μ-toluene) (3) is prepared in 62% isolated yield by addition of the neutral β-diketimine H[Me3NN] to copper t-butoxide in toluene. An X-ray structure of 3 shows that the bridging toluene ligand exhibits η2-bonding to each Cu center via four contiguous C atoms. Reaction of the dicopper 3 with 1 equiv. N2CPh2 provides {[Me3NN]Cu}2(μ-CPh2) (4) as purple crystals in 70% isolated yield. Dicopper carbene 4 possesses a Cu–Cu distance of 2.485(1) Å in the solid state and dissociates a [Me3NN]Cu fragment in arene solvents to provide low concentrations of [Me3NN]CuCPh2 (2) and [Me3NN]Cu(arene). DFT calculations performed on terminal carbene 2 and dicopper carbene 4 illustrate relationships between these two bonding modes and suggest electrophilic reactivity at the carbene carbon atom bound to Cu. Dicopper carbene 4 undergoes efficient carbene transfer to HCCPh and PPh3 resulting in the formation of 1,3,3-triphenylcyclopropene and Ph3PCPh2 while reaction with the isocyanide CNAr (Ar = 2,6-Me2C6H3) results in loss of the carbene as Ph2CCPh2. In each case, the [Me3NN]Cu fragment is trapped by the incoming nucleophile as the three-coordinate [Me3NN]Cu(L). Reaction of 4 with O2 rapidly generates benzophenone and {[Me3NN]Cu}2(μ-OH)2. 相似文献
5.
Treatment of [BzPh3P][AuCl2] with [Hg(x-C6H4NO2)2] (x = o, m, or p) gives anionic gold(I) complexes of the type [BzPh3P][Au(R)Cl](R = o-, m- or p-C6H4NO2, Bz = C6H5CH2). The chloro ligand in [Au(o-C6H4NO2)Cl]? can be replaced by bromo or iodo ligands by use of NaBr or NaI. The anions [Au(R)Cl]? react with neutral monodentate ligands, L, to give neutral mononuclear complexes [Au(R)L] (R = o-C6H4NO2, L = PPh3, AsPh3; R = m-C6H4NO2, L = PPh3) and with 1,2-bis(diphenylphosphino)ethane (dpe) to give [Au2(R)2(dpe)] (R = o-C6H4NO2). The corresponding [Au(p-C6H4NO2)Cl]? reacts with PPh3 or AsPh3 to give mixtures containing [AuClL]. The anionic ortho-nitrophenylgold(I) complex is much more stable than its meta- or para-nitrophenyl isomers. These are thought to be the first reports of nitrophenylgold(I) complexes. 相似文献
6.
Jun Luo Xi‐Geng Zhou Lin‐Hong Weng Xiu‐Feng Hou 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(10):m392-m395
Two new complexes, [Cu(C2N3)2(dien)] (dien is diethylenetriamine, C4H13N3), (I), and [Cu(C2N3)(trien)](C2N3) (trien is triethylenetetramine, C6H18N4), (II), have been characterized by single‐crystal X‐ray diffraction. Both complexes display a distorted tetragonal–pyramidal geometry. In (I), the Cu atom is coordinated in the basal plane by three diethylenetriamine N atoms [Cu—N = 2.000 (2), 2.004 (2) and 2.025 (2) Å] and one terminal N atom [Cu—N = 1.974 (2) Å] from one monodentate dicyanamide group, and in the apical position by one terminal N atom [Cu—N = 2.280 (2) Å] from the other monodentate dicyanamide group. In (II), the Cu atom is surrounded by four triethylenetetramine N atoms [Cu—N = 2.012 (2), 2.014 (2), 2.019 (2) and 2.031 (2) Å in the basal plane] and a terminal N atom [Cu—N = 2.130 (2) Å in the apical site] from one monodentate dicyanamide group. The other dicyanamide anion is not directly coordinated to the metal atom. In both (I) and (II), hydrogen‐bond interactions between the uncoordinated terminal N atoms of two dicyanamide ions and the amine H atoms lead to the formation of three‐dimensional networks. 相似文献
7.
Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12‐Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II)
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Thomas Brietzke Alexandra Kelling Uwe Schilde Wulfhard Mickler Hans‐Jürgen Holdt 《无机化学与普通化学杂志》2016,642(1):8-13
The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12‐tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane (L‐N4Me2) ligand, yielding complexes of the general formula [(L‐N4Me2)Ru(µ‐tape)M(L‐N4Me2)](ClO4)2(PF6)2 with M = Fe {[ 2 ](ClO4)2(PF6)2}, Co {[ 3 ](ClO4)2(PF6)2}, and Ni {[ 4 ](ClO4)2(PF6)2}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)‐ and platinum(II)‐dichloride [(bpy)2Ru(μ‐tape)PdCl2](PF6)2 {[ 5 ](PF6)2} and [(dmbpy)2Ru(μ‐tape)PtCl2](PF6)2 {[ 6 ](PF6)2}, respectively were also prepared. The molecular structures of the complex cations [ 2 ]4+ and [ 4 ]4+ were discussed on the basis of the X‐ray structures of [ 2 ](ClO4)4 · MeCN and [ 4 ](ClO4)4 · MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono‐ and homodinuclear ruthenium(II) complexes of the tape bridging ligand. 相似文献
8.
N. V. Khitrich I. I. Seifullina S. E. Nefedov A. V. Mazepa 《Russian Journal of Inorganic Chemistry》2006,51(7):1000-1008
The reaction between CoX2 (X = Br, I, NCS, NO3) and N,N,N′,N′-tetramethylthiuram disulfide is found to be a redox process. Irrespective of the anion, it yields cobalt(III) dimethyldithiocarbamate {Co(Me2Dtc)3}. The other products vary in number and composition: Me4Ditt[CoBr4] forms for X = Br; Me2Tmi[I3], S, and Co(Me2Dtc)3 · I2, for X = I; [Co(Me2Ditc)4](NCS)2, for X = NCS; CoSO4 · 7H2O and NO, for X = NO3 (Me4Ditt = 3,6-di(dimethyliminio)-1,2,4,5-tetrathian, Me2Tmi = dimethylthioxomethylideneimonium, and Me2Ditc = dimethyldithiocarbamatoisothiocyanate). The compounds have been characterized by chemical analysis, X-ray diffraction, mass spectrometry, conductivity measurements, IR and electronic spectroscopy, and magnetic measurements. The structure of Co(Me2Dtc)3 · I2 was determined by X-ray crystallography. 相似文献
9.
Shouwen Jin Dr. Daqi Wang Zhiwen Zheng Jie Chen Chao Feng Xianghua Ye Yiping Zhou 《无机化学与普通化学杂志》2010,636(8):1617-1624
Five novel coordination polymers, [(Cu(L1)2OH) · Cl · 3H2O] ( 1 ) [L1 = bis(N‐imidazolyl)methane], [Cd(L1)2(NCS)2] ( 2 ), [Zn(L1)2(NCS)2] ( 3 ), [Cu(L1)2(NO3)2] ( 4 ), and [Cu(L2)1.5(NCS)2] ( 5 ) [L2 = 1,4‐bis(N‐imidazolyl)butane] were obtained from self‐assembly of the corresponding metal salts with flexible ligands and their structures were fully characterized by X‐ray diffraction (XRD) analysis, Fourier Transform Infrared (FT‐IR) spectroscopy, elemental analysis and thermogravimetric (TGA) measurements. X‐ray diffraction analyses revealed that complexes 1 , 2 , 3 , and 4 exhibit 1D double‐stranded chain structures, which result from doubly bridged [CuOH], [M(NCS)2] (M = Cd, Zn), and [Cu(NO3)2] units, respectively. The polymeric copper complex 5 displays 1D ladder structure., These complexes, with the exception of complex 1 , are stable up to 300 °C. 相似文献
10.
L.V. Tatjanenko Yu.Sh. Moshkovsky I.A. Zakharova G. Ponticelli M. Massacesi G. Devoto 《Polyhedron》1985,4(1):159-162
The investigation of the inhibitory activity on the Ca,Mg-dependent ATP-ase substrate of some Cu(II) and Ni(II) complexes with polyamines and imidazole derivatives is reported. These results show that the Cu(II) complexes have high inhibitorial effect with the exception of the following very stable compounds: square planar [Cu(N-PropIm)2(NCS)2], distorted octahedral [Cu(bipy)2(NCS)2] and five coordinate [Cu(Me6tren)(NCS)] (SCN). The Ni(II) derivatives present a medium inhibitorial activity except to the stable tetrahedral [Ni(N-PropIm)2(NCS)2], hexacoordinate [Ni(dpt)(tn)(NCS)] (SCN) and fivecoordinate [Ni(dpt)(tn)]Br2 and [Ni(Me6tren)(NCS)] (SCN). An explanation of these conclusions is reported. 相似文献
11.
Electronic and ESR spectra of the complexes [Cu(II)(tpaso)4][Cu(I)Cl2]2,[Cu(tpaso)4](NO3)2 and [Cu(tpaso)4](ClO 相似文献
12.
Suman RoyTapan Kumar Mondal Partha MitraElena Lopez Torres Chittaranjan Sinha 《Polyhedron》2011,30(6):913-922
6-Aminocoumarin reacts with pyridine-2-carboxaldehyde and has synthesized N-[(2-pyridyl)methyliden]-6-coumarin (L). The ligand, L, reacts with [Cu(MeCN)4]ClO4/AgNO3 to synthesize Cu(I) and Ag(I) complexes of formulae, [Cu(L)2]ClO4 and [Ag(L)2]NO3, respectively. While similar reaction in the presence of PPh3 has isolated [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3. All these compounds are characterized by FTIR, UV-Vis and 1H NMR spectroscopic data. In case of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3, the structures have been confirmed by X-ray crystallography. The structure of the complexes are distorted tetrahedral in which L coordinates in a N,N′ bidentate fashion and other two coordination sites are occupied by PPh3. The ligand and the complexes are fluorescent and the fluorescence quantum yields of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3 are higher than [Cu(L)2]ClO4 and [Ag(L)2]NO3. Cu(I) complexes show Cu(II)/Cu(I) quasireversible redox couple while Ag(I) complexes exhibit deposition of Ag(0) on the electrode surface during cyclic voltammetric experiments. gaussian 03 computations of representative complexes have been used to determine the composition and energy of molecular levels. An attempt has been made to explain solution spectra and redox properties of the complexes. 相似文献
13.
《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1992,48(4):557-562
IR, EPR and electronic spectral studies have been made on a series of complexes with general formula [M(dien)L](BØ4)2nH2O (M = Cu(II), Zn(II), Cd(II), dien = N-(2-aminoethyl)-1,2-ethanediamine, L = ethanediamine (en), Me4en, Et2en, Me = methyl, Et = ethyl, BØ4 = tetraphenylborate, n = 0 or 2] taking copper(II) as a magnetic probe in polycrystalline and solution forms to obtain stereochemical information. A five-coordinate square-based pyramidal (SBP) geometry with CuN3N′2 moiety having moderately covalent metal-ligand σ-bonds is found to exist in unalkylated mixed ligand complexes. Among alkylated complexes [Cu/Cd(dien)(Me4en)](BØ4)2 is found to possess two species having tetrahedral and SBP with trigonal bipyramidal distortion geometries unlike the other alkylated complexes which have indicated the presence of one species having SBP coordination geometry with varying degrees of trigonal bipyramidal distortions and metal-ligand σ-bond strengths. EPR studies in dilute dmf and pyridine solutions of copper(II) complexes indicated the presence of solute-solvent interaction. 相似文献
14.
Aurel Tbcaru Rais Ahmad Khan Giulio Lupidi Claudio Pettinari 《Molecules (Basel, Switzerland)》2020,25(22)
Seeking to enrich the yet less explored field of scorpionate complexes bearing antioxidant properties, we, here, report on the synthesis, characterization and assessment of the antioxidant activity of new complexes derived from three scorpionate ligands. The interaction between the scorpionate ligands thallium(I) hydrotris(5-methyl-indazolyl)borate (TlTp4Bo,5Me), thallium(I) hydrotris(4,5-dihydro-2H-benzo[g]indazolyl)borate (TlTpa) and potassium hydrotris(3-tert-butyl- pyrazolyl)borate (KTptBu), and metal(II) chlorides, in dichloromethane at room temperature, produced a new family of complexes having the stoichiometric formula [M(Tp4Bo,5Me)2] (M = Cu, 1; Zn, 4; Cd, 7), [M(Tpa)2] (M = Cu, 2; Zn, 5; Cd, 8), [Cu(HpztBu)3Cl2] (3), [Zn(TptBu)Cl] (6) and [Cd(BptBu)(HpztBu)Cl] (9). The obtained metal complexes were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and elemental analysis, highlighting the total and partial hydrolysis of the scorpionate ligand TptBu during the synthesis of the Cu(II) complex 3 and the Cd(II) complex 9, respectively. An assessment of the antioxidant activity of the obtained metal complexes was performed through both enzymatic and non-enzymatic assays against 1,1-diphenyl-2-picryl- hydrazyl (DPPH·), 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+·), hydroxyl (HO·), nitric oxide (NO·), superoxide (O2−) and peroxide (OOH·) radicals. In particular, the complex [Cu(Tpa)2]⋅0.5H2O (2) exhibited significant antioxidant activity, as good and specific activity against superoxide (O2−·), (IC50 values equal to 5.6 ± 0.2 μM) and might be identified as auspicious SOD-mimics (SOD = superoxide dismutase). 相似文献
15.
Dr. I. Gănescu D. Oprescu Cs. Várhelyi 《Monatshefte für Chemie / Chemical Monthly》1974,105(3):525-534
Substitution reactions of anhydrous K3[Cr(NCS)6] with tertiary aromatic monoamines such as N,N-dimethylaniline and N,N-diethylaniline were carried out in the absence of solvents. The tertiary amines readily form compounds analogous to Reinecke salts,amine 2H[Cr(NCS)4(N,N-dimethylaniline)2] andamine 2H[Cr(NCS)4(N,N-Diethylaniline)2] respectively. The formula of the new complex anions was established by a series of double decomposition reactions with the hydrochlorides of some heterocyclic N-bases, alcaloids and cobalt(III)-ammine complexes. Some structural problems were resolved by UV and IR spectroscopic studies. 相似文献
16.
Three new μ‐oxamido‐bridged heterodinuclear copper (II)‐chromium (III) complexes formulated [Cu(Me2oxpn)Cr‐(L)2](NO3)3, where Me2oxpn denotes N,N'‐bis(3‐amino‐2, 2‐dimethylpropyl)oxamido dianion and L represents 5‐methyl‐1,10‐phenanthroline (Mephen), 4,7‐diphenyl‐1,10‐phenanthroline (Ph2phen) or 2,2′‐bipyridine (bpy), have been synthesized and characterized by elemental analyses, IR and electronic spectral studies, magnetic moments of room‐temperature and molar conductivity measurements. It is proposed that these complexes have oxamido‐bridged structures consisting of planar copper (II) and octahedral chromium (III) ions. The variable temperature magnetic susceptibilities (4.2–300 K) of complexes [Cu(Me2oxpn)Cr(Ph2phen)2](NO3)3 (1) and [Cu(Me2oxpn)Cr(Mephen)2] (NO3)3 (2) were further measured and studied, demonstrating the ferromagnetic interaction between the adjacent chromium (III) and copper (II) ions through the oxamido‐bridge in both complexes 1 and 2. Based on the spin Hamiltonian, ? = ‐ 2J?1 · ?2, the exchange integrals J were evaluated as + 21.5 an?1 for 1 and + 22.8 cm?1 for 2. 相似文献
17.
Shota Yamada Dr. Takeshi Matsumoto Prof. Dr. Ho-Chol Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8268-8278
The oxidation of [MII(3,5-DTBCat)(DTBbpy)] (M=Ni ( [Ni] ), Pd ( [Pd] ), and Pt ( [Pt] ); 3,5-DTBCat=3,5-di-tert-butylcatecholato; DTBbpy=4,4′-di-tert-butyl-2,2′-bipyridine) afforded the dimeric {[NiII(3,5-DTBSQ)(DTBbpy)](PF6)}2 ( {[Ni](PF6)}2 ; 3,5-DTBSQ=3,5-di-tert-butylsemiquinonato) and monomeric semiquinonato (SQ) complexes [MII(3,5-DTBSQ)(DTBbpy)](PF6) (M=Pd ( [Pd](PF6) ) and Pt ( [Pt](PF6) )). The negative solvatochromic properties of the SQ complexes allowed us to estimate the relative order of their dipole moments: [Pd](PF6) > [Pt](PF6) > {[Ni](PF6)}2 . The complexes [Pd](PF6) and [Pt](PF6) adopt monomeric structures and are stable in CH2Cl2 and toluene, whereas they gradually disproportionate at room temperature to [M] and 3,5-di-tert-butylbenzoquinone (3,5-DTBBQ) in polar solvents such as THF, MeOH, EtOH, DMF, or DMSO. The results of spectroscopic studies suggested that the oxidized nickel complex adopts a monomeric structure ( [Ni](PF6) ) in CH2Cl2, but a dimeric structure ( {[Ni](PF6)}2 ) in the other investigated solvents. In polar solvents, {[Ni](PF6)}2 may disproportionate to [Ni] and 3,5-DTBBQ at 323 K, thereby demonstrating a significant solvent- and metal-dependence in temperature. The relative activities of {[Ni](PF6)}2 and [M](PF6) toward disproportionation are related to the electrochemically estimated Kdis values in CH2Cl2 and DMF. The present work demonstrates that solvent polarity and the dipole moments of the SQ complexes promote disproportionation, which can be controlled by a judicious choice of the metal ion, solvent, and temperature. 相似文献
18.
Tapashi G. Roy Saroj K. S. Hazari Benu K. Dey Ashish Nath D. I. Kim E. H. Kim Y. C. Park 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(3-4):249-255
One isomer, LC of the isomeric Me8[14]anes, LA, LB and LC; on reaction with Ni(NCS)2 produces a six coordinate octahedral diisothiocyanato complex, [NiLC(NCS)2]. This complex undergoes axial substitution reactions with the small ligands to yield corresponding monosubstituted derivatives having general formula [NiLC(NCS)X] whereas X = Cl, Br, I, NO2 or NO3. The complexes have been characterized on the basis of analytical, spectroscopic, magnetic and conductance data. The structure of [NiLC(NCS)2] (triclinic, space group P?1, α = 8.0421(17) Å, β = 8.9085(18) Å, χ = 9.687(2) Å, α = 67.561(3) Å, β = 82,896(4) Å, ζ = 598.7(2) Å3, Z = 2, Dc = 1.352 mg/m3, μ(Mo Kα) = 1.003 mm?1) was confirmed by X-ray crystallography. 相似文献
19.
Cui Jianzhong Shi Wei Cheng Peng Liao Daizheng Yan Shiping Jiang Zonghui Wang Genglin Yao Xinkan Wang Honggen 《中国科学:化学(英文版)》2002,45(6):640-646
Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2 (4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2. 2425(4) nm,b = 1.0088(2) nm,c= 1.4665(3) nm, β= 125.32(3)δ Z = 4;R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of macrocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond. 相似文献
20.
Results are presented for mixed ligand copper(II) complexes of 3,3'-diaminodipropyl-amine and 1,3-diaminopropane studied by electron paramagnetic resonance. The spectra of the complexes in polycrystalline powder form and in frozen solutions of N,N'-dimethyl-formamide indicate that the complexes [Cu(dpt)tn]Cl2·H2O and [Cu(dpt)tn]Br2 have a square based pyramidal CuN5 chromophore and that the complexes [Cu(dpt)tn]I2 and [Cu(dpt)tn](ClO4)2 possess a compressed trigonal bipyramidal CuN5 chromophore. 相似文献