ja8b01876_si_002.cif (2 MB)
Download fileGround-State Copper(III) Stabilized by N‑Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity
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posted on 2018-05-11, 00:00 authored by 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 FurutaStable
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.