Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity
Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity
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DOI：
10.1021/jacs.8b01876
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发表时间：
2018-06-06
影响因子：
15
通讯作者：
Furuta, Hiroyuki
中科院分区：
文献类型：
--
作者：
Maurya, Yogesh Kumar;Noda, Katsuya;Furuta, Hiroyuki
合成了以 NNNC 配位核为卡巴咯基四齿大环配体支撑的稳定方形平面有机铜（III）配合物（CuNCC2、CuNCC4 和 CuBN），并通过包括 X 射线晶体学分析在内的光谱手段阐明了其结构。基于其独特的平面结构、X射线吸收/光电子能谱特征以及与温度无关的抗磁性，这些有机铜配合物可以优选地被认为是新型有机铜(III)物种。配合物高价 Cu(III) 态的显着稳定性源自于咔咯修饰骨架的独特 NNNC 配位衍生的闭壳电子结构，这与具有 NNNN 核的常规咔咯铜 (II) 配合物的氧化还原非无害自由基性质形成鲜明对比。所提出的结构得到了 DFT (B3LYP) 计算的支持。此外，通过 CuNCC4 的单电子氧化获得了通过内部碳连接的 pi 层压二聚体结构。我们设想，对这些有机金属咔咯络合物的分子轨道能量和氧化还原曲线的精确控制最终可能导致尚未探索的高价金属物种的分离及其有机金属反应的发展。
Stable square planar organocopper(III) complexes (CuNCC2, CuNCC4, and CuBN) supported by carbacorrolebased 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 corrolemodified 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 pi-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.