X-ray crystal structure* and kinetics of oxidation ...
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| Title | X-ray crystal structure* and kinetics of oxidation of 1,4,8,11-tetraazaundecanenickel(II), [Ni-II(2,3,2-tet)](2+) by peroxodisulphate: formation of a stable non-macrocyclic nickel(III) polyamine |
| Author(s) | B. Bernard, R. Haines, J. Rowley |
| Journal | Transition Metal Chemistry |
| Date | 2001 |
| Volume | 26 |
| Issue | 1-2 |
| Start page | 164 |
| End page | 169 |
| Abstract | 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 tervalent state. The reaction follows a second order rate law, first order in [Ni-II(2,3,2-tet)](2+) and first order in peroxodisulphate. The activation enthalpy and entropy are 55 +/- 3 kJ mol(-1) and -38 +/- 10 J K-1 mol(-1) respectively. The X-ray crystal structure of the [Ni-II(2,3,2-tet)](2+) cation is also described. The title compound crystallizes in the monoclinic space group P2(1)/n. The cation has a slightly distorted square planar structure, with the bite angle of the 5-membered chelate rings being slightly less than 90 degrees, and that of the 6-membered chelate ring being correspondingly greater than 90 degrees. |
| ISSN | 0340-4285 |
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