作者:V. Mahesh Krishnan、Dimitar Y. Shopov、Caitlin J. Bouchey、Wilson D. Bailey、Riffat Parveen、Bess Vlaisavljevich、William B. Tolman
DOI:10.1021/jacs.0c13470
日期:2021.3.10
Formal Cu(III) complexes bearing an oxygen-based auxiliary ligand ([CuOR]2+, R = H or CH2CF3) were stabilized by modulating the donor character of supporting ligand LY (LY = 4-Y, N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide, Y = H or OMe) and/or the basicity of the auxiliary ligand, enabling the first characterization of these typically highly reactive cores by NMR spectroscopy and X-ray
通过调节支持配体 L Y ( L Y = 4 - Y , N , N '-双(2,6-二异丙基苯基)-2,6-吡啶二甲酰胺, Y = H 或 OMe) 和/或辅助配体的碱度, 能够通过 NMR 光谱和 X 首次表征这些典型的高反应性核- 射线晶体学。观察到苯酚底物在溶液中的寿命延长和 PCET 速率降低。核磁共振光谱证实了S= 0 配合物的基态,X 射线结构显示缩短的 Cu-配体键距离与理论非常吻合。