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The structures of trans-[Co-III(cyclam)(NCS)(2)](NCS) and of [Co-II(Me(4)cyclam)(NCS)](2)[Co(NCS)(4)]. MeOH have been established by X-ray diffraction methods. The solvatochromic behavior of the trans-[Co(cyclam)(NCS)(2)](+) cation in several binary aqueous solvent mixtures is reported. Transfer che...
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The kinetics of nucleophilic substitution by cyanide ion at the bis-(2,3,5,6-tetrakis (2-pyridyl)pyrazine)iron(II) cation, [Fe(tppz)(2)](2+) have been measured, and the crystal structure of the product [Fe(tppz)-(CN)(3)](-) anion is reported. The kinetics of oxidation of bath [Fe(tppz)(2)](2+) and [...
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Solvent effects on the kinetics of peroxodisulphate oxidation of dicyanobis(2,2-bipyridyl)iron(II), [Fe(bipy)2(CN)2], in aqueous methanol have been analysed into initial state and transition state components; the latter dominate the observed reactivity trend.
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The kinetic pattern for reaction of [Fe(CN)5(3,5-Me2py)]3? and [Fe(CN)5,(3-CNpy)]3? with a range of incomlng groups, in water and in 40% glycol and 40% t-butyl alcohol, is consistent with the operation of a D mechanism under all the condi...
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The decomposition kinetics of the [Ag(II)L]2+ cation (where L = [15]aneN4) has been studied as a function of [H+] and temperature, in aqueous perchlorate media (ionic strength = 1.00 mol dm-3). The decomposition follows the second-order rate, law, Rate = k[H+][Ag(II)L2+], where k = (6.65 +/- 0.11) x...
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The nickel(II) complex of the deprotonated pendant-arm macrocycle 5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane-4,11-diace tate (L-2)(2-) has been structurally characterized by X-ray crystallography. The Ni(II)L-2 complex crystallizes in the monoclinic system, space group P2(1)/c, wi...
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Rate constants for the aquation of tris(5-nitro-1,10-phenanthroline)iron(II) have been determined in a wide range of binary aqueous mixtures. The results are presented and discussed in terms of correlation diagrams involving the excess molar Gibbs function of mixing for the binary mixtures. The beha...
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A simple method for the preparation of cis-dichloro(1,4,7-triazacyclononane)platinum(II), cis-Pt(tacn)Cl2 is presented, together with the results of screening the compound against the K-562 (leukemia) and SK-OV-3 (ovarian) human cancer cell lines. While the compound shows no activity against K-562 c...
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While macrocyclic ligands are well-known to stabilize tervalent nickel, it is very unusual to form stable nickel(III)-amine species in aqueous solution. We describe the kinetics of oxidation of 1,4,8,11-tetraazaundecanenickel(II), [Ni-II(2,3,2-tet)](2+) by peroxodisulphate in aqueous solution to the...
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Dependences of rate constants on pressure (in aqueous solution up to 1.25 kbar) are reported for peroxodisulphate oxidation of hexacyanoferrate(TI), tris(2,2'-bipyridyl)iron(II), tris(l,10-phenanthroline)iron(II), bis(l,4,7-triazacyclononane)nickel(II) and bis(l,2-ethanediamine)cysteinatocobalt(III)...
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Rates of reaction of [Fe(bipy)3]2+ with cyanide ion in binary aqueous solvent mixtures containing ethylene glycol glycerol, acetonitrile, dimethyl sulphoxide (dmso), or tris (dimethylamino)phosph ine oxide (tdpo), and with hydroxide ion in binary aqueous solvent mixtures contai...
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