美国圣路易斯华盛顿大学William B. Tolman团队表征了[CuOR]2+核的结构。 相关研究成果于2021年2月23日发表在《美国化学会杂志》。

通过调节支持配体LY（LY=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）的给体性质和/或辅助配体的碱度，稳定了含有氧基辅助配体（[CuOR]2+，R=H或CH2CF3）的Cu（III）配合物。通过核磁共振波谱和X射线晶体学首次对这些典型的高活性核进行了表征。

研究观察到苯酚底物提高了PCET在溶液中的寿命，减慢了PCET的速率。核磁共振谱证实了配合物的S=0基态，X射线结构显示铜-配体键距缩短，与理论相符。

附：英文原文

Title: Structural Characterization of the [CuOR]2+ Core

Author: V. Mahesh Krishnan, Dimitar Y. Shopov, Caitlin J. Bouchey, Wilson D. Bailey, Riffat Parveen, Bess Vlaisavljevich, William B. Tolman

Issue&Volume: February 23, 2021

Abstract: 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 crystallography. Enhanced lifetimes in solution and slowed rates of PCET with a phenol substrate were observed. NMR spectra corroborate the S = 0 ground states of the complexes, and X-ray structures reveal shortened Cu–ligand bond distances that match well with theory.

DOI: 10.1021/jacs.0c13470

Source: https://pubs.acs.org/doi/10.1021/jacs.0c13470