Reduction reaction of the Copper(II) complex bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile

Atsutoshi Yamada; Yuki Watanabe; Kyoko Noda; Sumitaka Itoh; Koji Ishihara; Masahiko Inamo; Refat Moustafa Hassan; Hideo D. Takagi

doi:10.1007/s10953-014-0154-7

Reduction reaction of the Copper(II) complex bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile

Atsutoshi Yamada, Yuki Watanabe, Kyoko Noda, Sumitaka Itoh, Koji Ishihara, Masahiko Inamo, Refat Moustafa Hassan, Hideo D. Takagi

School of Advanced Science and Engineering

Research output: Contribution to journal › Article › peer-review

Abstract

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 (δH∗= 33.3 ± 1.0 kJ·mol^-1, δS∗= 86 ± 5 J·mol^-1·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°) in solution whereas it is merely 17.14° in the crystal.

Original language	English
Pages (from-to)	1479-1486
Number of pages	8
Journal	Journal of Solution Chemistry
Volume	43
Issue number	9-10
DOIs	https://doi.org/10.1007/s10953-014-0154-7
Publication status	Published - 2014 Oct 21

Keywords

Acetonitrile
Cu(II)(pitn)
Cyclic voltammetry
Decemethylferrocene
Rate constants

ASJC Scopus subject areas

Biophysics
Biochemistry
Molecular Biology
Physical and Theoretical Chemistry

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Reduction reaction of the Copper(II) complex bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile. / Yamada, Atsutoshi; Watanabe, Yuki; Noda, Kyoko; Itoh, Sumitaka; Ishihara, Koji; Inamo, Masahiko; Hassan, Refat Moustafa; Takagi, Hideo D.

In: Journal of Solution Chemistry, Vol. 43, No. 9-10, 21.10.2014, p. 1479-1486.

Research output: Contribution to journal › Article › peer-review

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title = "Reduction reaction of the Copper(II) complex bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile",

abstract = "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 (δH∗= 33.3 ± 1.0 kJ·mol-1, δS∗= 86 ± 5 J·mol-1·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°) in solution whereas it is merely 17.14° in the crystal.",

keywords = "Acetonitrile, Cu(II)(pitn), Cyclic voltammetry, Decemethylferrocene, Rate constants",

author = "Atsutoshi Yamada and Yuki Watanabe and Kyoko Noda and Sumitaka Itoh and Koji Ishihara and Masahiko Inamo and Hassan, {Refat Moustafa} and Takagi, {Hideo D.}",

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AU - Yamada, Atsutoshi

AU - Watanabe, Yuki

AU - Noda, Kyoko

AU - Itoh, Sumitaka

AU - Ishihara, Koji

AU - Inamo, Masahiko

AU - Hassan, Refat Moustafa

AU - Takagi, Hideo D.

PY - 2014/10/21

Y1 - 2014/10/21

N2 - 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 (δH∗= 33.3 ± 1.0 kJ·mol-1, δS∗= 86 ± 5 J·mol-1·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°) in solution whereas it is merely 17.14° in the crystal.

AB - 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 (δH∗= 33.3 ± 1.0 kJ·mol-1, δS∗= 86 ± 5 J·mol-1·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°) in solution whereas it is merely 17.14° in the crystal.

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KW - Cu(II)(pitn)

KW - Cyclic voltammetry

KW - Decemethylferrocene

KW - Rate constants

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