Abstract Two polypyridine complexes containing μ-OH, μ-O2 dicobalt(III) cores, [(TPA)CoIII(μ-OH)(μ-O2) CoIII(TPA)](ClO4)3 and [(BPMEN)CoIII(μ-OH)(μ-O2)CoIII(BPMEN)](ClO4)3 (TPA = tris(2-pyridylmethyl)amine, BPMEN = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)ethane-1,2-diamine), have previously been reported as inactive in the light-driven water oxidation reaction (ACS Catal., 2016, 6, 5062−5068). Herein, another dicobalt(III) compound, μ-OH, μ-O2-[{(enN4)2Co2}](ClO4)3 (enN4 = 1,6-bis(2-pyridyl-2,5-diazaocta-2,6-diene), with a similar core structure was synthesized, characterized, and applied to the light-driven water oxidation reaction. Collective experiments showed that the complex itself was also inactive in the light-driven water oxidation, and that the activity observed originated from Co(II) impurities. This research establishes that complexes possessing a μ-OH, μ-O2 dicobalt(III) core structure are not appropriate choices for true molecular catalysts of water oxidation.

中文翻译：

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含有μ-OH、μ-O 2 二钴(iii)核的聚吡啶络合物的水氧化催化能力

摘要 两种含有 μ-OH、μ-O2 二钴 (III) 核、[(TPA)CoIII(μ-OH)(μ-O2) CoIII(TPA)](ClO4)3 和 [(BPMEN)CoIII(μ -OH)(μ-O2)CoIII(BPMEN)](ClO4)3 (TPA = 三(2-吡啶基甲基)胺，BPMEN = N,N'-二甲基-N,N'-双(吡啶-2-基甲基)乙烷-1,2-二胺），之前曾报道在光驱动的水氧化反应中无活性（ACS Catal., 2016, 6, 5062-5068）。在此，另一种二钴(III)化合物，μ-OH，μ-O2-[{(enN4)2Co2}](ClO4)3 (enN4 = 1,6-bis(2-pyridyl-2,5-diazaocta-2, 6-diene), 具有类似的核心结构被合成、表征并应用于光驱动水氧化反应。集体实验表明配合物本身在光驱动水氧化中也没有活性, 观察到的活性起源于来自 Co(II) 杂质。