Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity

Journal of the American Chemical Society
Yogesh Kumar MauryaHiroyuki Furuta

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 une...Continue Reading

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Citations

Sep 16, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Maryne DuvalDidier Bourissou
Oct 31, 2018·Chemistry, an Asian Journal·Shota OoiAtsuhiro Osuka
Jul 1, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Xinyu Xu
Feb 25, 2021·Chemistry, an Asian Journal·Yogesh Kumar MauryaHiroyuki Furuta
May 20, 2021·Topics in Current Chemistry·Poornenth Pushpanandan, Mangalampalli Ravikanth
May 1, 2021·Angewandte Chemie·Mai OdajimaHiroshi Shinokubo
Nov 12, 2019·Journal of the American Chemical Society·Ida M DiMucciKyle M Lancaster
Oct 3, 2019·Inorganic Chemistry·Timothy J ZerkWilliam B Tolman
Nov 7, 2019·Journal of the American Chemical Society·Yutao RaoJianxin Song
Jan 31, 2020·Journal of the American Chemical Society·Liliia MoshniahaMarcin Stępień
Dec 31, 2021·Journal of the American Chemical Society·Jinseok KimDongho Kim

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