Journal of the American Chemical Society p. 5497 - 5505 (1984)
Update date:2022-08-05
Topics:
Kimura, Eiichi
Machida, Ryosuke
Kodama, Mutsuo
Substituted and unsubstituted macrocyclic dioxo pentaamines, 1,4,7,10,13-pentaazacyclohexadecane-14,16-dione, form stable 1:1 square-pyramidal complexes with Ni(II) and Cu(II), which possess two deprotonated amide donors in equatorial positions.The high-spin Ni(II) complexes show a very low Ni(II,III) redox potential of +0.24 V vs.SCE and are easily oxidized chemically or electrochemically to Ni(III) complexes.Moreover, the Ni(II) complexes react with molecular oxygen to form 1:1 Ni(II)-O2 adducts in aqueous solution, as established by a combination of polarographic, spectrophotometric, and manometric methods.Comparative studies with relevant pentadentate macrocyclic polyamine complexes revealed that the two deprotonated amide groups and the fifth amine donor incorporated in the 16-membered macrocyclic frame are essential for the formation of the Ni(II)-O2 adducts.The oxygen uptake reaction is first order in
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