New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(Disalicylidene)diamine Complexes

Kazutaka Asami, Kazuaki Tsukidate, Satoshi Iwatsuki, Fumito Tani, Satoru Karasawa, Linus Chiang, Tim Storr, Fabrice Thomas, Yuichi Shimazaki

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

The neutral and one-electron oxidized Cu(II) six-membered chelate 1,3-Salcn (1,3-Salcn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-cyclohexanediamine) complexes have been investigated and compared with the five-membered chelate 1,2-Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)- diamine) complexes. Cyclic voltammetry of Cu(1,3-Salcn) showed two reversible redox waves at 0.48 and 0.68 V, which are only 0.03 V higher than those of Cu(1,2-Salcn). Reaction of Cu(1,3-Salcn) with 1 equiv of AgSbF6 afforded the oxidized complex which exists as a ligand-based radical species in solution and in the solid state. The X-ray crystal structure of the oxidized complex, [Cu(1,3-Salcn)]SbF6, exhibited an asymmetric metal binding environment with a longer Cu-O bond and quinoid distortion in the phenolate moiety on one side, demonstrating at least partial ligand radical localization in the solid state. The ligand oxidation is also supported by XPS and temperature dependent magnetic susceptibility. The electronic structure of the [Cu(1,3-Salcn)]+ complex was further probed by UV-vis-NIR, resonance Raman, and electron paramagnetic resonance (EPR) measurements, and by theoretical calculations, indicating that the phenoxyl radical electron is relatively localized on one phenolate moiety in the molecule. The reactivity of [Cu(1,3-Salcn)]+ with benzyl alcohol was also studied. Quantitative conversion of benzyl alcohol to benzaldehyde was observed, with a faster reaction rate in comparison with [Cu(1,2-Salcn)]+. The kinetic isotope effect (KIE = k(H)/k(D)) of benzyl alcohol oxidation by [Cu(1,3-Salcn)]+ was estimated to be 13, which is smaller than the value reported for [Cu(1,2-Salcn)]+. The activation energy difference between [Cu(1,2-Salcn)]+ and [Cu(1,3-Salcn)]+ was in good agreement with the energy calculated from KIE. This correlation suggests that the Cu(II)-phenoxyl radical species, characterized for [Cu(1,2-salcn)] + is more reactive for hydrogen abstraction from benzyl alcohol in comparison to the 1:1 mixture of Cu(III)-phenolate and Cu(II)-phenoxyl radical species, [Cu(1,2-Salcn)]+. Thus, the Cu(II)-phenoxyl radical species accelerates benzyl alcohol oxidation in comparison with the Cu(III)-phenolate ground state complex, in spite of the similar activated intermediate and oxidation pathway.

Original languageEnglish
Pages (from-to)12450-12461
Number of pages12
JournalInorganic chemistry
Volume51
Issue number22
DOIs
Publication statusPublished - Nov 19 2012

Fingerprint

Benzyl Alcohol
Diamines
diamines
Electronic structure
Copper
reactivity
electronic structure
alcohols
copper
Electrons
Oxidation
Ligands
oxidation
electrons
chelates
ligands
solid state
Magnetic susceptibility
Isotopes
Ground state

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(Disalicylidene)diamine Complexes. / Asami, Kazutaka; Tsukidate, Kazuaki; Iwatsuki, Satoshi; Tani, Fumito; Karasawa, Satoru; Chiang, Linus; Storr, Tim; Thomas, Fabrice; Shimazaki, Yuichi.

In: Inorganic chemistry, Vol. 51, No. 22, 19.11.2012, p. 12450-12461.

Research output: Contribution to journalArticle

Asami, K, Tsukidate, K, Iwatsuki, S, Tani, F, Karasawa, S, Chiang, L, Storr, T, Thomas, F & Shimazaki, Y 2012, 'New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(Disalicylidene)diamine Complexes', Inorganic chemistry, vol. 51, no. 22, pp. 12450-12461. https://doi.org/10.1021/ic3018503
Asami, Kazutaka ; Tsukidate, Kazuaki ; Iwatsuki, Satoshi ; Tani, Fumito ; Karasawa, Satoru ; Chiang, Linus ; Storr, Tim ; Thomas, Fabrice ; Shimazaki, Yuichi. / New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(Disalicylidene)diamine Complexes. In: Inorganic chemistry. 2012 ; Vol. 51, No. 22. pp. 12450-12461.
@article{4980cfdc20414793b8cd685ec5468847,
title = "New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(Disalicylidene)diamine Complexes",
abstract = "The neutral and one-electron oxidized Cu(II) six-membered chelate 1,3-Salcn (1,3-Salcn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-cyclohexanediamine) complexes have been investigated and compared with the five-membered chelate 1,2-Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)- diamine) complexes. Cyclic voltammetry of Cu(1,3-Salcn) showed two reversible redox waves at 0.48 and 0.68 V, which are only 0.03 V higher than those of Cu(1,2-Salcn). Reaction of Cu(1,3-Salcn) with 1 equiv of AgSbF6 afforded the oxidized complex which exists as a ligand-based radical species in solution and in the solid state. The X-ray crystal structure of the oxidized complex, [Cu(1,3-Salcn)]SbF6, exhibited an asymmetric metal binding environment with a longer Cu-O bond and quinoid distortion in the phenolate moiety on one side, demonstrating at least partial ligand radical localization in the solid state. The ligand oxidation is also supported by XPS and temperature dependent magnetic susceptibility. The electronic structure of the [Cu(1,3-Salcn)]+ complex was further probed by UV-vis-NIR, resonance Raman, and electron paramagnetic resonance (EPR) measurements, and by theoretical calculations, indicating that the phenoxyl radical electron is relatively localized on one phenolate moiety in the molecule. The reactivity of [Cu(1,3-Salcn)]+ with benzyl alcohol was also studied. Quantitative conversion of benzyl alcohol to benzaldehyde was observed, with a faster reaction rate in comparison with [Cu(1,2-Salcn)]+. The kinetic isotope effect (KIE = k(H)/k(D)) of benzyl alcohol oxidation by [Cu(1,3-Salcn)]+ was estimated to be 13, which is smaller than the value reported for [Cu(1,2-Salcn)]+. The activation energy difference between [Cu(1,2-Salcn)]+ and [Cu(1,3-Salcn)]+ was in good agreement with the energy calculated from KIE. This correlation suggests that the Cu(II)-phenoxyl radical species, characterized for [Cu(1,2-salcn)] + is more reactive for hydrogen abstraction from benzyl alcohol in comparison to the 1:1 mixture of Cu(III)-phenolate and Cu(II)-phenoxyl radical species, [Cu(1,2-Salcn)]+. Thus, the Cu(II)-phenoxyl radical species accelerates benzyl alcohol oxidation in comparison with the Cu(III)-phenolate ground state complex, in spite of the similar activated intermediate and oxidation pathway.",
author = "Kazutaka Asami and Kazuaki Tsukidate and Satoshi Iwatsuki and Fumito Tani and Satoru Karasawa and Linus Chiang and Tim Storr and Fabrice Thomas and Yuichi Shimazaki",
year = "2012",
month = "11",
day = "19",
doi = "10.1021/ic3018503",
language = "English",
volume = "51",
pages = "12450--12461",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "22",

}

TY - JOUR

T1 - New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(Disalicylidene)diamine Complexes

AU - Asami, Kazutaka

AU - Tsukidate, Kazuaki

AU - Iwatsuki, Satoshi

AU - Tani, Fumito

AU - Karasawa, Satoru

AU - Chiang, Linus

AU - Storr, Tim

AU - Thomas, Fabrice

AU - Shimazaki, Yuichi

PY - 2012/11/19

Y1 - 2012/11/19

N2 - The neutral and one-electron oxidized Cu(II) six-membered chelate 1,3-Salcn (1,3-Salcn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-cyclohexanediamine) complexes have been investigated and compared with the five-membered chelate 1,2-Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)- diamine) complexes. Cyclic voltammetry of Cu(1,3-Salcn) showed two reversible redox waves at 0.48 and 0.68 V, which are only 0.03 V higher than those of Cu(1,2-Salcn). Reaction of Cu(1,3-Salcn) with 1 equiv of AgSbF6 afforded the oxidized complex which exists as a ligand-based radical species in solution and in the solid state. The X-ray crystal structure of the oxidized complex, [Cu(1,3-Salcn)]SbF6, exhibited an asymmetric metal binding environment with a longer Cu-O bond and quinoid distortion in the phenolate moiety on one side, demonstrating at least partial ligand radical localization in the solid state. The ligand oxidation is also supported by XPS and temperature dependent magnetic susceptibility. The electronic structure of the [Cu(1,3-Salcn)]+ complex was further probed by UV-vis-NIR, resonance Raman, and electron paramagnetic resonance (EPR) measurements, and by theoretical calculations, indicating that the phenoxyl radical electron is relatively localized on one phenolate moiety in the molecule. The reactivity of [Cu(1,3-Salcn)]+ with benzyl alcohol was also studied. Quantitative conversion of benzyl alcohol to benzaldehyde was observed, with a faster reaction rate in comparison with [Cu(1,2-Salcn)]+. The kinetic isotope effect (KIE = k(H)/k(D)) of benzyl alcohol oxidation by [Cu(1,3-Salcn)]+ was estimated to be 13, which is smaller than the value reported for [Cu(1,2-Salcn)]+. The activation energy difference between [Cu(1,2-Salcn)]+ and [Cu(1,3-Salcn)]+ was in good agreement with the energy calculated from KIE. This correlation suggests that the Cu(II)-phenoxyl radical species, characterized for [Cu(1,2-salcn)] + is more reactive for hydrogen abstraction from benzyl alcohol in comparison to the 1:1 mixture of Cu(III)-phenolate and Cu(II)-phenoxyl radical species, [Cu(1,2-Salcn)]+. Thus, the Cu(II)-phenoxyl radical species accelerates benzyl alcohol oxidation in comparison with the Cu(III)-phenolate ground state complex, in spite of the similar activated intermediate and oxidation pathway.

AB - The neutral and one-electron oxidized Cu(II) six-membered chelate 1,3-Salcn (1,3-Salcn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-cyclohexanediamine) complexes have been investigated and compared with the five-membered chelate 1,2-Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)- diamine) complexes. Cyclic voltammetry of Cu(1,3-Salcn) showed two reversible redox waves at 0.48 and 0.68 V, which are only 0.03 V higher than those of Cu(1,2-Salcn). Reaction of Cu(1,3-Salcn) with 1 equiv of AgSbF6 afforded the oxidized complex which exists as a ligand-based radical species in solution and in the solid state. The X-ray crystal structure of the oxidized complex, [Cu(1,3-Salcn)]SbF6, exhibited an asymmetric metal binding environment with a longer Cu-O bond and quinoid distortion in the phenolate moiety on one side, demonstrating at least partial ligand radical localization in the solid state. The ligand oxidation is also supported by XPS and temperature dependent magnetic susceptibility. The electronic structure of the [Cu(1,3-Salcn)]+ complex was further probed by UV-vis-NIR, resonance Raman, and electron paramagnetic resonance (EPR) measurements, and by theoretical calculations, indicating that the phenoxyl radical electron is relatively localized on one phenolate moiety in the molecule. The reactivity of [Cu(1,3-Salcn)]+ with benzyl alcohol was also studied. Quantitative conversion of benzyl alcohol to benzaldehyde was observed, with a faster reaction rate in comparison with [Cu(1,2-Salcn)]+. The kinetic isotope effect (KIE = k(H)/k(D)) of benzyl alcohol oxidation by [Cu(1,3-Salcn)]+ was estimated to be 13, which is smaller than the value reported for [Cu(1,2-Salcn)]+. The activation energy difference between [Cu(1,2-Salcn)]+ and [Cu(1,3-Salcn)]+ was in good agreement with the energy calculated from KIE. This correlation suggests that the Cu(II)-phenoxyl radical species, characterized for [Cu(1,2-salcn)] + is more reactive for hydrogen abstraction from benzyl alcohol in comparison to the 1:1 mixture of Cu(III)-phenolate and Cu(II)-phenoxyl radical species, [Cu(1,2-Salcn)]+. Thus, the Cu(II)-phenoxyl radical species accelerates benzyl alcohol oxidation in comparison with the Cu(III)-phenolate ground state complex, in spite of the similar activated intermediate and oxidation pathway.

UR - http://www.scopus.com/inward/record.url?scp=84869426758&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84869426758&partnerID=8YFLogxK

U2 - 10.1021/ic3018503

DO - 10.1021/ic3018503

M3 - Article

C2 - 23113569

AN - SCOPUS:84869426758

VL - 51

SP - 12450

EP - 12461

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 22

ER -