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Host-guest interactions between alpha- and beta-cyclodextrins and nickel(II) polyazamacrocycles bearing aliphatic pendant arms (n-butyl, n-octyl and n-dodecyl) have been investigated, using redox kinetics as a probe, to estimate binding constants. Electrospray mass spectrometry shows the formation o...
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The binuclear complex bis-(chloropalladium(II))-tetrakis(2-pyridyl)pyrazine chloride, [Pd2Cl2(tppz)]Cl-2 has been synthesized and characterized. The complex shows solvatochromic behaviour in aqueous DMSO solvent mixtures. The kinetics of nucleophilic substitution of the complex by guanine is reporte...
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The outer-sphere oxidation of the nickel(II) complex of the deprotonated pendant-arm macrocycle, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-1-acetate, [NiL1(OH2)](+) by bis-(1,4,7-triazacyclononane)nickel(III), [Ni(tacn)(2)](3+) has been studied in aqueous perchlorate media. The rea...
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Three nickel(II) pentaazamacrocycles bearing pendant alkyl tails have been synthesized, and the crystal structure of one (bearing an octyl tail) is reported. The redox potentials of the complexes, for oxidation of the nickel(II) centre, is 0.72 V (versus S. H. E.) in all cases, indicating that the p...
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The pendant-arm macrocycle, meso-5,5,7,12,12,14-hexamethy 1,4,8,11-tetraazacyclotetradecane- 1,8-di-(1-methylnaphthalene) has been synthesized and its single crystal structure determined. The molecule crystallizes in a primitive monoclinic cell, with the space group P2(1)/a (#14). The cell dimension...
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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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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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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...
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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...
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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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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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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 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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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 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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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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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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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 ...
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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 ...