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...

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...

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...

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...

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...

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_...

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...

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 ...

The dissociative step of a dissociative, or D, substitution mechanism exhibits a volume of activation, V₁, which is independent of the nature of the incoming nucleophile. For the reaction of [Fe(CN)₅(3,5Me₂-py)]^3?(3,5Me₂-py = 3,5-d...

The kinetics of oxidation of bis(1,4,7-triazacyclononane)nickel(II), [Ni(tacn)2]2+, by the peroxodisulphate anion has been studied in water as a function of S2O82- concentration and temperature. The reaction is first order in both the nickel(II) complex and S2O82-, with a second-order rate constant ...

In an attempt to generate new platinum compounds that may be effective in the treatment of cancer, as well as having a lower toxicity than traditional platins and being orally viable, we are studing the synthesis and reactivity of platinum complexes of tetraazamacrocycles bearing carboxylato pendant...

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 [...

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...

The kinetics of oxidation of 1,4,8,11-tetraazacyclotetradecane-5,7-diamidonickel(II) ('nickel dioxocyclam') by peroxodisulfate have been measured in a range of binary aqueous solvent mixtures. Reaction rates are retarded by the presence of organic co-solvents, indicative of destabilization of the tr...