Nickel macrocyclic complexes octahedral species

SlOO proteins, calcium binding, 46 451-456 Spruhtrocken process, 4 26 Square-planar complexes, 4 157-164 octahedral, compared, 4 162-174 in solution, 34 270-271 Square-planar iridium complexes, 44 295, 297 Square-planar nickel macrocyclic complexes equilibrium with octahedral species, 44 116-118... 

Macrocyclic complexes (continued) nickel(II), 44 93-94 eatalysis, 44 119-125 configurational isomerization, 44 126 electrochemical properties, 44 112-113 electronic absorption spectra, 44 108-112 reactions, 44 118-119 square-planar and octahedral species, 44 116-118... 

The reaction of superoxotitanium(IV) with a number of substrates has been monitored by stopped-flow techniques/ In 1 M perchloric acid, the oxidation of iodide and bromide proceeded with second-order ratde constants of 1.1 x 10 M s and 2M s respectively. It is proposed that the reduction of superoxotitanium(IV) proceeds by a one-electron mechanism. Based on proton dependences, the species TiO " is more reactive than the protonated form Ti02(0H)2. The chromium chelate, bis(2-ethyl-2-hydroxybutyrato)oxochro-mate(V), is reduced by iodide, generating a Cr(IV) intermediate. The reaction is considered to proceed through formation of an iodine atom (T) for which both Cr(V) and Cr(IV) compete. In aqueous solution, [Co(EDTA)] forms a tight ion pair with I . Upon irradiation of this ion pair at 313 nm, reduction of [Co(EDTA)] to [Co(EDTA)] occurs with oxidation of 1 to IJ. The results may be interpreted on the basis of a mechanism in which [Co(EDTA)] and V are the primary photoproducts where the latter subsequently disproportionate to I3 and 1 . The kinetics and mechanism of the oxidation of 1 by a number of tetraaza macrocyclic complexes of Ni(III) have been reported. Variations in rate constants and reaction pathways are attributable to structural differences in the macrocyclic ligands. Of interest is the fact that with some of the Ni(III) complexes, spectrophotometric evidence has been obtained for an inner-sphere process with characterization of the transient [Ni(III) L(I)] intermediates. Iodide has also been used as a reductant for a nickel(III) complex of R-2-methyl-1,4,7-triazacylononane. In contrast to the square-planar macrocycles, the octahedral... 

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