Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Picobiology Institute, Graduate School of Life Science, University of Hyogo, RSC-UH LP Center, Koto 1-1-1, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan.
J Inorg Biochem. 2017 Dec;177:375-383. doi: 10.1016/j.jinorgbio.2017.08.016. Epub 2017 Sep 1.
Copper(II) complexes supported by N-tridentate ligands, consisting of a rigid cyclic diamine (8-membered cyclic-diamine; L8 or 7-membered cyclic-diamine; L7) and a 2-(2-pyridyl)ethyl (-CHCHPy) group, were synthesized and structurally characterized. Reaction of the copper(II) complexes and cumene hydroperoxide (CmOOH) in the presence of triethylamine in CHCN gave the corresponding cumylperoxide complexes L8CuOOCm and L7CuOOCm. The UV-vis and EPR spectra suggested that L8CuOOCm takes a tetrahedrally distorted structure, whereas L7CuOOCm has a planar geometry in solution. Resonance Raman spectra of these alkylperoxide complexes indicated that the O-O stretching vibration energy of L8CuOOCm (ν=878cm) is somewhat lower than that of L7CuOOCm (ν=881cm). Such a difference in O-O bond strength is reflected to the reactivity difference of these two alkylperoxide complexes. Namely, the reactivity L8CuOOCm toward CHD (1,4-cyclohexadiene) as well as solvent molecule (CHCN) is higher than that of L7CuOOCm due to the weaker O-O bond of the former complex as compared to that of the latter complex. Geometric effects on the reactivity induced by the supporting ligands are discussed.
合成并结构表征了由刚性环状二胺（8 元环状二胺；L8 或 7 元环状二胺；L7）和 2-(2-吡啶基)乙基（-CHCHPy）基团组成的配体支持的铜（II）配合物。在 CHCN 中存在三乙胺的情况下，铜（II）配合物与过氧化枯烯（CmOOH）反应得到相应的过氧化枯烯配合物 L8CuOOCm 和 L7CuOOCm。UV-vis 和 EPR 光谱表明，L8CuOOCm 采取四面体扭曲结构，而 L7CuOOCm 在溶液中具有平面几何形状。这些烷基过氧化物配合物的共振拉曼光谱表明，L8CuOOCm 的 O-O 伸缩振动能（ν=878cm）略低于 L7CuOOCm 的 O-O 伸缩振动能（ν=881cm）。这种 O-O 键强度的差异反映在这两个烷基过氧化物配合物的反应性差异上。也就是说，L8CuOOCm 对 CHD（1,4-环己二烯）以及溶剂分子（CHCN）的反应性高于 L7CuOOCm，这是由于前者配合物的 O-O 键比后者配合物的 O-O 键弱。讨论了配体支持对反应性的几何效应。
