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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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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 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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Preparations of iron(II) complexes of bi-, tri-, quadri-, quinque-, and sexi-dentate Schiff bases are reported. The Schiff-base ligands are derived from pyridine-2-carbaldehyde, phenyl 2-pyridyl ketone, pyridine-2,6-dicarb-aldehyde. or 2,6-diacetylpyridine, and appropriate amines. All these complexe...
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Solvent effects on the discriminatory properties of the transient [Fe(CN)5]3? intermediate in the dissociative (D) substitution at the complex ions [Fe(CN)5L]3?(L = 3- or 4-cyanopyridine) are described. The solvents employed are methanol?, ethanol?,...
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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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Kinetic data are reported for ring opening of benzocyclobutene-1,2-dione, 3-phenylcyclobutene-1,2-dione, 4-methoxy-3-phenylcyclobutene-1,2-dione, and 3,4-dimethoxycyclobutene-1,2-dione with the zerovalent platinum complexes [Pt(trans-PhCHCHPh)(PPh3)2] and [Pt(PhCCPh)(PPh...
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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...