Reduction Reaction of the Copper(II) Complex Bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile
The reduction reaction of the Cu(II)-pitn complex (pitn = 1,3-di(pyridine-2-carboxaldimino)propane) by decamethylferrocene [Fe(Cp*)2] was examined in acetonitrile. The observed pseudo-first-order rate constants exhibited saturation kinetics with increasing excess amount of [Fe(Cp*)2]. Detailed analy...
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Published in | Journal of solution chemistry Vol. 43; no. 9-10; pp. 1479 - 1486 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
01.10.2014
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Subjects | |
Online Access | Get full text |
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Summary: | The reduction reaction of the Cu(II)-pitn complex (pitn = 1,3-di(pyridine-2-carboxaldimino)propane) by decamethylferrocene [Fe(Cp*)2] was examined in acetonitrile. The observed pseudo-first-order rate constants exhibited saturation kinetics with increasing excess amount of [Fe(Cp*)2]. Detailed analyses revealed that the reaction is controlled by a structural change prior to the electron transfer step, rather than a conventional bimolecular electron transfer process preceded by ion pair (encounter complex) formation. The rate constant for the structural change was estimated to be 275 + or - 13 s-1 at 298 K ( Delta H* = 33.3 + or - 1.0 kJ times mol-1, Delta S* = 86 + or - 5 J times mol-1 times K-1), which is the fastest among gated reactions involving CuN4 complexes. It was confirmed by EPR measurement and Conflex calculations that the dihedral angle between the two N-N planes is significantly large (40[degrees]) in solution whereas it is merely 17.14[degrees] in the crystal. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 content type line 23 ObjectType-Feature-2 |
ISSN: | 0095-9782 1572-8927 |
DOI: | 10.1007/s10953-014-0248-2 |