Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles

Synthesis, Characterization, and Redox Reactivity

Yogesh Kumar Maurya, Katsuya Noda, Kazuhisa Yamasumi, Shigeki Mori, Tomoki Uchiyama, Kazutaka Kamitani, Tomoyasu Hirai, Kakeru Ninomiya, Maiko Nishibori, Yuta Hori, Yoshihito Shiota, Kazunari Yoshizawa, Masatoshi Ishida, Hiroyuki Furuta

研究成果: ジャーナルへの寄稿記事

7 引用 (Scopus)

抄録

Stable square planar organocopper(III) complexes (CuNCC2, CuNCC4, and CuBN) supported by carbacorrole-based tetradentate macrocyclic ligands with NNNC coordination cores were synthesized, and their structures were elucidated by spectroscopic means including X-ray crystallographic analysis. On the basis of their distinct planar structures, X-ray absorption/photoelectron spectroscopic features, and temperature-independent diamagnetic nature, these organocopper complexes can be preferably considered as novel organocopper(III) species. The remarkable stability of the high-valent Cu(III) states of the complexes stems from the closed-shell electronic structure derived from the peculiar NNNC coordination of the corrole-modified frameworks, which contrasts with the redox-noninnocent radical nature of regular corrole copper(II) complexes with an NNNN core. The proposed structure was supported by DFT (B3LYP) calculations. Furthermore, a π-laminated dimer architecture linked through the inner carbons was obtained from the one-electron oxidation of CuNCC4. We envisage that the precise manipulation of the molecular orbital energies and redox profiles of these organometallic corrole complexes could eventually lead to the isolation of yet unexplored high-valent metal species and the development of their organometallic reactions.

元の言語英語
ページ(範囲)6883-6892
ページ数10
ジャーナルJournal of the American Chemical Society
140
発行部数22
DOI
出版物ステータス出版済み - 6 6 2018

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Organometallics
Ground state
Oxidation-Reduction
Copper
Shells (structures)
X ray absorption
Molecular orbitals
Photoelectrons
X-Rays
Discrete Fourier transforms
Dimers
Electronic structure
Ligands
X rays
Oxidation
Carbon
Electrons
Metals
Temperature
corrole

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

これを引用

Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles : Synthesis, Characterization, and Redox Reactivity. / Maurya, Yogesh Kumar; Noda, Katsuya; Yamasumi, Kazuhisa; Mori, Shigeki; Uchiyama, Tomoki; Kamitani, Kazutaka; Hirai, Tomoyasu; Ninomiya, Kakeru; Nishibori, Maiko; Hori, Yuta; Shiota, Yoshihito; Yoshizawa, Kazunari; Ishida, Masatoshi; Furuta, Hiroyuki.

:: Journal of the American Chemical Society, 巻 140, 番号 22, 06.06.2018, p. 6883-6892.

研究成果: ジャーナルへの寄稿記事

Maurya, Yogesh Kumar ; Noda, Katsuya ; Yamasumi, Kazuhisa ; Mori, Shigeki ; Uchiyama, Tomoki ; Kamitani, Kazutaka ; Hirai, Tomoyasu ; Ninomiya, Kakeru ; Nishibori, Maiko ; Hori, Yuta ; Shiota, Yoshihito ; Yoshizawa, Kazunari ; Ishida, Masatoshi ; Furuta, Hiroyuki. / Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles : Synthesis, Characterization, and Redox Reactivity. :: Journal of the American Chemical Society. 2018 ; 巻 140, 番号 22. pp. 6883-6892.
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abstract = "Stable square planar organocopper(III) complexes (CuNCC2, CuNCC4, and CuBN) supported by carbacorrole-based tetradentate macrocyclic ligands with NNNC coordination cores were synthesized, and their structures were elucidated by spectroscopic means including X-ray crystallographic analysis. On the basis of their distinct planar structures, X-ray absorption/photoelectron spectroscopic features, and temperature-independent diamagnetic nature, these organocopper complexes can be preferably considered as novel organocopper(III) species. The remarkable stability of the high-valent Cu(III) states of the complexes stems from the closed-shell electronic structure derived from the peculiar NNNC coordination of the corrole-modified frameworks, which contrasts with the redox-noninnocent radical nature of regular corrole copper(II) complexes with an NNNN core. The proposed structure was supported by DFT (B3LYP) calculations. Furthermore, a π-laminated dimer architecture linked through the inner carbons was obtained from the one-electron oxidation of CuNCC4. We envisage that the precise manipulation of the molecular orbital energies and redox profiles of these organometallic corrole complexes could eventually lead to the isolation of yet unexplored high-valent metal species and the development of their organometallic reactions.",
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T2 - Synthesis, Characterization, and Redox Reactivity

AU - Maurya, Yogesh Kumar

AU - Noda, Katsuya

AU - Yamasumi, Kazuhisa

AU - Mori, Shigeki

AU - Uchiyama, Tomoki

AU - Kamitani, Kazutaka

AU - Hirai, Tomoyasu

AU - Ninomiya, Kakeru

AU - Nishibori, Maiko

AU - Hori, Yuta

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Ishida, Masatoshi

AU - Furuta, Hiroyuki

PY - 2018/6/6

Y1 - 2018/6/6

N2 - Stable square planar organocopper(III) complexes (CuNCC2, CuNCC4, and CuBN) supported by carbacorrole-based tetradentate macrocyclic ligands with NNNC coordination cores were synthesized, and their structures were elucidated by spectroscopic means including X-ray crystallographic analysis. On the basis of their distinct planar structures, X-ray absorption/photoelectron spectroscopic features, and temperature-independent diamagnetic nature, these organocopper complexes can be preferably considered as novel organocopper(III) species. The remarkable stability of the high-valent Cu(III) states of the complexes stems from the closed-shell electronic structure derived from the peculiar NNNC coordination of the corrole-modified frameworks, which contrasts with the redox-noninnocent radical nature of regular corrole copper(II) complexes with an NNNN core. The proposed structure was supported by DFT (B3LYP) calculations. Furthermore, a π-laminated dimer architecture linked through the inner carbons was obtained from the one-electron oxidation of CuNCC4. We envisage that the precise manipulation of the molecular orbital energies and redox profiles of these organometallic corrole complexes could eventually lead to the isolation of yet unexplored high-valent metal species and the development of their organometallic reactions.

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