ISSN:
1432-1327
Keywords:
Key words Nickel complex
;
DNA cleavage
;
O2 activation
;
Biomimetic chemistry
;
Macrocyclic polyamine
Source:
Springer Online Journal Archives 1860-2000
Topics:
Biology
,
Chemistry and Pharmacology
Notes:
Abstract Novel potentially five-coordinate pyridyl–pendant dioxocyclam [1-(2-pyridyl)methyl-5,7-dioxo-1,4,8,11-tetraazacyclotetradecane (H2L) and its homologs (6-methyl and 6,6-dimethyl derivatives)] have been synthesized to study nickel(II) complexation. A purple nickel(II) complex with a deprotonated amide (NiHL) was isolated from aqueous equimolar solution of H2L and Ni(ClO4)2. A yellow nickel(II) complex with two deprotonated amides (NiL) was crystallized from an H2O/CH3CN solution of H2L and Ni(OH)2. The X-ray crystal study of NiL showed a square-planar nickel(II) complex with the pyridyl–pendant remaining uncoordinated. It is concluded from the visible absorption and NMR study of NiL in aqueous solution that the four-coordinate NiL is in equilibrium with a five-coordinate square-pyramidal nickel(II) complex with the apical coordination of the pyridyl–pendant. A voltammetric study disclosed a low nickel(II/III) redox potential of +0.29 V vs SCE for NiL at pH 9.5 and 25 °C with 0.10 M Na2SO4. The nickel(II) complex NiL absorbed an equimolar amount of O2 at pH 9.5 and 25 °C, and the O2 was activated to cleave plasmid DNA.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/s007750050108
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