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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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Rate laws and rate constants are reported for the two stages of the reactions of [Fe(L?L)2(CN)2](L?L = 1,10-phenanthroline, 5-chloro-1,10-phenanthroline, or 2,2-bipyridyl) with cyanide ion in aqueous solution. The preparation of [Fe(5NO2-phen?CN)2(5NO...
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The structure of the title compound has been determined by X-ray crystallography. The octahedral arrangement of ligands about the iron(II) centre is somewhat distorted, with the axial NC-Fe-CN bond angle being 174.3(4)degrees. The oxidation of the tricyano-2,2',6',2 '-terpyridylferrate(II) anion by ...
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Features a study that examined the kinetics of oxidation of the nickel (II) tetraazamacrocyclic complex, 5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetraazacyclotetradecane-1-acetate, which bears one pendant acetato group to the nickel (III) state. Discussion on the use of the resulting nickel (III) macroc...
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This paper reviews the synthesis of pendant-arm macrocycles, and the structure and some properties of their first row transition metal complexes. The article covers the period 1997 to 2000, since a thorough review had previously been published, to 1997. The focus of this paper is on tri- and tetraaz...
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The kinetics of oxidation of several nickel(II) tetraazamacrocycles by the peroxydisulphate anion have been studied in water and in binary aqueous mixtures. The reactions proceed via an ion-pairing pre-equilibrium, followed by metal ion-assisted peroxy-bond fissure within the ion-pair solvent shell ...