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 |
| 巻 | 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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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
}
TY - JOUR
T1 - Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles
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.
AB - 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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U2 - 10.1021/jacs.8b01876
DO - 10.1021/jacs.8b01876
M3 - Article
VL - 140
SP - 6883
EP - 6892
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 22
ER -