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^*

^*Corresponding author for this work

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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10.1007/s10953-014-0154-7

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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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doi = "10.1007/s10953-014-0154-7",

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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.

KW - Acetonitrile

KW - Cu(II)(pitn)

KW - Cyclic voltammetry

KW - Decemethylferrocene

KW - Rate constants

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

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