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1.
In the Ni(II) complex of a reinforced tetramine macrocycle, equipped with both a sulfonamide pendant arm and a naphthalene fragment, light emission of the fluorophore is pH-controlled, as a result of a change of the geometry of the complex. 相似文献
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Dramatically enhanced carbon acidity of the nitrobenzyl fragment in a nickel(II) scorpionate complex
The -CH(2)- group of the 2-nitrobenzyl pendant arm of the scorpionate complex I deprotonates in basic aqueous solution (pK(a) = 10.6), due to the coordination of the nitronate group to the nickel(II) center. Metal coordination enhances 2-nitrobenzene acidity by 10 orders of magnitude. [reaction: see text] 相似文献
4.
Boca R Gembický M Herchel R Haase W Jäger L Wagner C Ehrenberg H Fuess H 《Inorganic chemistry》2003,42(22):6965-6967
Triethylenetetramine (L(4)) was used as a tetradentate blocking ligand that, after complexation with Ni(II), leaves two sites ready for ligation with tricyanomethanide. The formed binuclear complex [L(4)Ni(NCC(CN)CN)(2)NiL(4)](ClO(4))(2) exhibits a ferromagnetic coupling with J/hc = +0.15 cm(-1) and g(Ni) = 2.126; below 16 K, a ferromagnetic ordering is evidenced by ac magnetic susceptibility (both in-phase and out-of-phase), magnetization, field-cooled magnetization, and zero-field-cooled magnetization measurements. 相似文献
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Novel macrocyclic bis(disulfide)tetramine ligands and several Cu(II) and Ni(II) complexes of them with additional ligands have been synthesized by the oxidative coupling of linear tetradentate N2S2 tetramines with iodine. Facile demetalation of the Ni(II) oxidation products affords the free 20-membered macrocycles meso-9 and rac-9 and the 22-membered macrocycle 16, all of which are potentially octadentate N4S4 ligands. X-ray structure analyses reveal distinctly different conformations for the two isomers of 9; meso-9 shows a stepped conformation in profile with the disulfide groups corresponding to the rise of the step, whereas rac-9 exhibits a V conformation with the disulfide groups near the vertex of the V. No metal complexes of rac-9 have been isolated. Crystallographic studies of three Cu(II) complexes reveal that depending upon the size of the macrocyclic ligand and the nature of the additional ligands (I-, NCO-, and CH3CN), the Cu(II) coordination geometry shows considerable variation (plasticity), with substantial changes in the Cu(II)-disulfide bonding. Thus, a diiodide salt contains six-coordinate Cu(II) to which all four bridging disulfide sulfur atoms form strong equatorial bonds. In contrast, isocyanato complexes of the 20- and 22-membered macrocycles exhibit trigonal-bipyramidal Cu(II) and distorted cis-octahedral Cu(II) geometries, respectively, having only one and no short equatorially bound sulfur atoms. The coordination geometry of the latter complex can also be described as four-coordinate seesaw with two semicoordinated S(disulfide) ligands. Disulfide-->Cu(II) ligand-to-metal charge transfer absorptions of both isocyanato-containing Cu(II) species appear too weak to observe, probably because of poor overlap of the sulfur orbitals with the Cu(II) d-vacancy. The dual disulfide-bridged Ni(II) units of the crystallographically characterized octahedral Ni(II) complex of meso-9 with axial iodide and acetonitrile ligands promote substantial antiferromagnetic coupling (J = -13.0(2) cm-1). 相似文献
7.
Chernyad"ev A. Yu. Ustynyuk Yu. A. Aleksandrov G. G. Sidorov A. A. Novotortsev V. M. Ikorskii V. N. Nefedov S. E. Eremenko I. L. Moiseev I. I. 《Russian Chemical Bulletin》2001,50(7):1336-1338
Russian Chemical Bulletin - 相似文献
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Transition Metal Chemistry - After the publication of this article ‘Bis-chelates of nickel(II) and copper(II) with an O,S-donor piperazine ligand,’ it came to our attention that... 相似文献
9.
A. S. Kutsenko O. M. Burin S. M. Maloletov L. V. Tsymbal Ya. D. Lampeka 《Theoretical and Experimental Chemistry》1997,33(3):138-141
A novel polymeric material having nonlinear optical properties has been prepared from the diglycidyl ether of bisphenol A
and a macrocyclic complex of nickel(II). It has been shown that relatively high levels of third-order nonlinear susceptibility
of polymers can be obtained without the use of highly conjugated systems.
L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Nauka Prospect, Kiev 252039,
Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 3, pp. 165–169, May–June, 1997. 相似文献
10.
The ligand tris(2-hydroxyiminopropyl)amine (Ox(3)H(3)) binds to nickel(II) in multiple protonation states. In the neutral state, the X-ray crystal structure of the monomeric complex [Ni(Ox(3)H(3))(NO(3))(H(2)O)](NO(3)).(H(2)O), 1, has six-coordinate pseudo-octahedral geometry, with binding of the amine and three oxime nitrogens, a nitrate, and a water. In the mono-deprotonated form, the X-ray crystal structure shows a dimer, [Ni(Ox(3)H(2))(CH(3)CN)](2)(ClO(4))(2), 2, which has bridging oximate groups and a Ni-Ni distance of 3.575 A. The fully deprotonated complex, 3, shows significantly low Ni(II) oxidation potentials at -390 and +165 mV (versus Fc(+)/Fc). Complex 3 shows reactivity when exposed to O(2), consuming multiple O(2) equivalents and turning from the purple 3 to a dark brown complex, 4. Complex 4 has an EPR spectrum consistent with Ni(III), but spin quantitation accounts for only about 10% of the total Ni, consistent with turnover of the Ni oxidation states. This Ni(II)/O(2) system oxidizes triphenylphosphine to its oxide, with incorporation of the isotopic label from O(2). 相似文献
11.
The structure of the complex [Ni(hmt)(NCS)2(H2O)2]n, assembled by hexamethylenetetramine (hmt) and octahedral Ni(II), is reported. Crystal data: Fw 351.07, a=9.885(10) Å, b=12.06(1) Å, c=12.505(8) Å, β=114.41(4)°, V=1357(1) Å3, Z=4, space group=C2/c, T=173 K, λ(Mo−K)=0.71070 Å, ρcalc=1.718 gcm−1, μ=17.44 cm−1, R=0.099, Rw=0.145. The tetrahedral assembling template effect of the hmt molecule is completed by two coordination bonds and two hydrogen interactions. The UV–vis absorption spectrum of this complex [Ni(hmt)(NCS)2(H2O)2]n with a two-dimensional network is determined in the range of 5000–35000 cm−1 at room temperature. The observed spectrum is discussed and explained perfectly by the scaling radial theory proposed by us. The two-dimensional structure has no apparent effects on the d–d transitions of the central Ni(II) ion. The IR spectrum and the GT curve of the complex were also measured and clearly reflect its structural properties. 相似文献
12.
Nahid Shahabadi Soheila Kashanian Marzieh Khosravi Maryam Mahdavi 《Transition Metal Chemistry》2010,35(6):699-705
The water-soluble Ni(II) complex, [Ni(bipy)2(phen-dione)](OAc)2·2H2O (bipy = 2,2′-bipyridine and phen-dione = 1,10-phenanthroline-5,6-dione) has been synthesized and characterized by physico-chemical
and spectroscopic methods. The binding interactions of this complex with calf thymus DNA (CT-DNA) were investigated using
fluorimetry, spectrophotometry, circular dichroism and viscosimetry. In fluorimetric studies, the enthalpy and entropy of
the reaction between the complex and CT-DNA showed that the reaction is exothermic (ΔH = −123.9 kJ mol−1; ΔS = −323.5 J mol−1 K−1). The competitive binding studies showed that the complex could not release methylene blue completely. The complex showed
absorption hyperchromism in its UV–Vis spectrum with DNA. The calculated binding constant, K
b obtained from UV–Vis absorption studies was 2 × 105 M−1. Moreover, the complex induced detectable changes in the CD spectrum of CT-DNA, as well as changes in its viscosity. The
results suggest that this nickel(II) complex interact with CT-DNA via a groove-binding mode. 相似文献
13.
Chattopadhyay S Drew MG Diaz C Ghosh A 《Dalton transactions (Cambridge, England : 2003)》2007,(24):2492-2494
A novel single thiocyanato-bridged one-dimensional polymer, [NiL(NCS)(micro-NCS)]n (L = N1-(1-pyridin-2-yl-ethylidine)propane-1,3-diamine) has been synthesized and characterized by X-ray crystallography and a variable temperature magnetic study; the compound is a metamagnet with a Neél temperature (T(N)) of 3.5 K. 相似文献
14.
T. Gangaiah P. Ramadevi G. R. K. Naidu K. Venugopal Chetty 《Journal of Radioanalytical and Nuclear Chemistry》1991,150(1):177-182
Isotopic exchange behaviour of bis(diethyldithio carbamate) nickel(II) complex with nickel(II) in chloroform and methanol medium was studied. The studies were carried out at different temperatures varying the concentration of both metal ion and the complex. The results show that the complex is labile in the kinetic sense. Increase in temperature increases the isotopic exchange rate. The increase in concentration also results in enhancement of the rate of reaction. 相似文献
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The influence of a water-acetone solvent on the stability of nickel(II) complexes with glycylglycine
V. A. Isaeva V. V. Naumov V. A. Sharnin 《Russian Journal of Coordination Chemistry》2009,35(11):868-870
The stability constants of nickel(II) complexes with glycylglycine in water-acetone mixtures (mole fraction of acetone X = 0–0.40) were determined by potentiometric titration at 298 K and an ionic strength of 0.1 M (NaClO4). With an increase in the content of the organic cosolvent, nickel(II) glycylglycinates become more stable, mainly because
of the better coordination of the ligand through the carboxy group. 相似文献
17.
T. Gangaiah P. Ramadevi T. Balaji G. R. K. Naidu 《Journal of Radioanalytical and Nuclear Chemistry》1993,173(1):137-140
Isotope exchange behavior of bis-resacetophenone phenylhydrazone) nickel(II) complex with nickel(II) in tri-n-butyl phosphate and methanol medium has been studied. The studies were carried out at different temperatures varying the concentration of both metal ion and the complex. The results show that the complex is labile in the kinetic sense. Increase in temperature increases the isotope exchange rate. The increase in concentration also results in an enhancement of the rate of reaction. 相似文献
18.
Polymeric copper(II) and nickel(II) complexes of a binucleating tetraoxime macrocycle, 6,6-methylene-bis[1,12-di(hydroximino)- 2,3;9,10-dibenzo-1,11-diaza-4,8-dithiacyclotridecane] (H4L), have been prepared and characterised by elemental analysis, magnetic moments, i.r., uv/vis., and e.p.r. spectral studies. I.r. spectra show that the ligand acts in a tetradentate manner and coordinates via N, S and O donor atoms. The geometry of the resulting metal chelates is discussed with the help of magnetic and spectroscopic measurements. The elemental analyses, stoichiometry and the spectroscopic data of the complexes indicate that the copper(II) and nickel(II) ions are coordinated by the coordination environment of the ligand. The spectral data suggest a distorted tetragonal geometry for polymeric copper(II), and nickel(II) ions in the complexes. The stoichiometry of the metal-to- H4L ratio of complexes (2) and (3), prepared from CuCl2 and NiCl2 respectively, was 3:1, suggesting the formation of polymeric species. 相似文献
19.
Xin Wang 《Journal of organometallic chemistry》2005,690(12):2934-2940
Preparation of two imidazolium salts, two monomeric nickel(II) and one cobalt(II) complexes bearing imidazolium ligands is described, The solid-state structures of these compounds have determined by single-crystal X-ray diffraction. After activation with methylaluminoxane (MAO) the nickel complexes show moderate catalytic activities of up to 6 × 105 g PE mol−1Ni h−1 for polymerization of ethylene. Catalytic activities, molecular weights have been investigated under the various reaction conditions. 相似文献