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 a...

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Published inJournal of solution chemistry Vol. 43; no. 9-10; pp. 1479 - 1486
Main Authors Yamada, Atsutoshi, Watanabe, Yuki, Noda, Kyoko, Itoh, Sumitaka, Ishihara, Koji, Inamo, Masahiko, Hassan, Refat Moustafa, Takagi, Hideo D.
Format Journal Article
LanguageEnglish
Published Boston Springer US 01.10.2014
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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 ± 13 s −1 at 298 K (∆ H * = 33.3 ± 1.0 kJ·mol −1 , ∆ S * = 86 ± 5 J·mol −1 ·K −1 ), which is the fastest among gated reactions involving CuN 4 complexes. It was confirmed by EPR measurement and Conflex calculations that the dihedral angle between the two N–N planes is significantly large (40°) in solution whereas it is merely 17.14° in the crystal.
ISSN:0095-9782
1572-8927
DOI:10.1007/s10953-014-0154-7