Nickel(II) and Copper(II) complexes of tetra-and pentadentatethioether-oxime ligands have been synthesized. An extraordinary range ofproperties are exhibited by the complexes. The tetradentate thioether-oximecomplexes of copper(II) form... more
Nickel(II) and Copper(II) complexes of tetra-and pentadentatethioether-oxime ligands have been synthesized. An extraordinary range ofproperties are exhibited by the complexes. The tetradentate thioether-oximecomplexes of copper(II) form axial/equatorial dimeric complexes in the solidstate. These complexes exhibit weak ferromagnetic coupling betweenadjacent copper(II) ions. ESR spectra reveal that the dimer is broken insolution, and indeed the ESR spectra reveal tetragonal symmetry about thecopper(II) ions in the tetradentate thioether-oximes. The electrochemistry of these complexes supports the fact that oxime-containing ligands stabilizecopper(II). Nickel(II) forms a wide range of structures with the tetradentate ligands; the geometries vary from low-spin square planar to high-spin trinuclear complexes. The nickel(II) ions in trimeric complexes are disposed at the corners of an isosceles triangle and couple to each other through weak antiferromagnetic interactions. The electrochemi...
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An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely... more
An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
With the use of various methods, including EXAFS, the Ni‐Fe center was found to contain the nickel atom surrounded by nitrogen and sulfur donor atoms and the attached Fe 4 S 4 cluster [1]. Upon treatment of dehydrogenase with carbon... more
With the use of various methods, including EXAFS, the Ni‐Fe center was found to contain the nickel atom surrounded by nitrogen and sulfur donor atoms and the attached Fe 4 S 4 cluster [1]. Upon treatment of dehydrogenase with carbon monooxide, the Ni‐Fe center is reduced and attaches CO to produce the so-called Ni‐ Fe‐C center [2]. The spatial arrangement of the donor environment of nickel in the active centers of Ni‐CO dehydrogenases have not been clearly identified, and the experimental data may be interpreted in terms of both the four-coordinate nickel atom in the square-planar surroundings and the five-coordinate state of the nickel atom [3]. Besides, the oxidation state of nickel neither in the Ni‐Fe center of free Ni‐CO dehydrogenase nor in the Ni‐Fe center at different stages of the catalyzed reactions is determined definitely. The CO adducts with the Ni(I) compounds may be the intermediates in the aforementioned reactions. The progress in the structural study of these unique...
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Three new nickel(II) complexes with ligands 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (Pdto) and dithiosemicarbazone of 4,7-dithiadecane-2,9-dione (DtdtzH2) of composition Ni(Pdto)(H2O)2(ClO4)2, Ni(DtdtzH2)(ClO4)2 and Ni(Dtdtz) were... more
Three new nickel(II) complexes with ligands 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (Pdto) and dithiosemicarbazone of 4,7-dithiadecane-2,9-dione (DtdtzH2) of composition Ni(Pdto)(H2O)2(ClO4)2, Ni(DtdtzH2)(ClO4)2 and Ni(Dtdtz) were prepared, their molecular structures, spectral and redox-properties were studied. The possibilities of chemical reduction of Ni(Pdto)(H2O)2(ClO4)2 to nickel(I) and nickel(0) species and the reaction of nickel(I) complex with CO were shown, which may be described as the modeling of one of the stages of reactions with CO on active Ni-Fe-site of Ni-CO-dehydrogenases. It was found that Ni(DtdtzH2)(ClO4)2 reacted with (Et4N)2[Fe4S4(SBz)4] (BzSH = C6H5 CH2SH) forming adduct. In the row of studied complexes Ni(Pdto) (H2O)2(ClO4)2 may be described as the best structural model of Ni-Fe-site of Ni-CO-dehydrogenases on the redox properties.
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1,3-bis{2-(4-methylpyridyl)imino}isoindoline (4-MeInH) reacts with copper(II) acetate and 2,4,6-trimercaptotriazine (H3TMTA) to yield [Cu(4-MeIn)]3(TMTA), a trinuclear propeller complex composed of three Cu(4-MeIn) “blades” coordinated to... more
1,3-bis{2-(4-methylpyridyl)imino}isoindoline (4-MeInH) reacts with copper(II) acetate and 2,4,6-trimercaptotriazine (H3TMTA) to yield [Cu(4-MeIn)]3(TMTA), a trinuclear propeller complex composed of three Cu(4-MeIn) “blades” coordinated to a 2,4,6-trimercaptotriazine (TMTA) “hub”. Each copper(II) center is coordinated via a exocyclic sulfur and a ring nitrogen from TMTA. Although the trimer is infinitely stable in the solid state, dark green solutions fade over time to produce
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Bis(o-aminobenzaldehyde)thiocarbohydrazone (HL) forms with copper(II) nitrate a tetranuclear complex [Cu2(L)(NO3)3]2·2H2O, in which two dinuclear units are joined by nitrate bridges. The dihydrazone ligand behaves ditopically, providing... more
Bis(o-aminobenzaldehyde)thiocarbohydrazone (HL) forms with copper(II) nitrate a tetranuclear complex [Cu2(L)(NO3)3]2·2H2O, in which two dinuclear units are joined by nitrate bridges. The dihydrazone ligand behaves ditopically, providing NNS and NNN binding sites, with the four coppers essentially in a square-pyramidal geometry. The tetranuclear molecule displays intramolecular magnetic interactions, with the antiferromagnetic exchange (−2J=210(1)cm−1) between the copper(II) ions within each dinuclear moiety
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The quadridentate dipyridyl-dithioether ligand 1, 8-bis(2′-pyridyl)-3, 6-dithiaoctane (Pdto) forms a pseudooctahedral complex with nickel(II). Blue [Ni(Pdto)(OH2)2](ClO4)2 crystallizes in the space group P/21c, with a = 11.677(5), b =... more
The quadridentate dipyridyl-dithioether ligand 1, 8-bis(2′-pyridyl)-3, 6-dithiaoctane (Pdto) forms a pseudooctahedral complex with nickel(II). Blue [Ni(Pdto)(OH2)2](ClO4)2 crystallizes in the space group P/21c, with a = 11.677(5), b = 13.255(2), c = 15.804(4)Å, β = 107.45(3)° and Z = 4. The ligand is folded about the Ni(II) ion so that the water ligands are cis within an O2S2 plane and the
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Structural, magnetic and related attributes of some oximate-bridged tetranuclear nickel(ii) rhombs and a dinuclear congenerElectronic supplementary information (ESI) available: mass spectra, χT vs. T, response of magnetic properties, low-lying spin levels and UV-VIS data. See http://www.rsc.org/s...more