The reaction of 3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane (DAPTA) with metal salts of Cu^II or Na^I/Ni^II under mild conditions led to the oxidized phosphane derivative 3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane‐5‐oxide (DAPTA=O) and to the first examples of metal complexes based on the DAPTA=O ligand, that is, [Cu^II(μ‐CH₃COO)₂(κO‐DAPTA=O)]₂ (1) and [Na(1κOO′;2κO‐DAPTA=O)(MeOH)]₂(BPh₄)₂ (2). The catalytic activity of 1 was tested in the Henry reaction and for the aerobic 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO)‐mediated oxidation of benzyl alcohol. Compound 1 was also evaluated as a model system for the catechol oxidase enzyme by using 3,5‐di‐tert‐butylcatechol as the substrate. The kinetic data fitted the Michaelis–Menten equation and enabled the obtainment of a rate constant for the catalytic reaction; this rate constant is among the highest obtained for this substrate with the use of dinuclear Cu^II complexes. DFT calculations discarded a bridging mode binding type of the substrate and suggested a mixed‐valence Cu^II/Cu^I complex intermediate, in which the spin electron density is mostly concentrated at one of the Cu atoms and at the organic ligand.

中文翻译：

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基于3,7-二乙酰基-1,3,7-三氮杂-5-磷酸双环[3.3.1]壬烷-5-氧化物的铜（II）和钠（I）配合物：合成，表征和催化活性

3,7-二乙酰基-1,3,7-三氮杂-5-磷杂双环[3.3.1]壬烷（DAPTA）与Cu ^II或Na ^I / Ni ^II的金属盐在温和条件下的反应导致氧化膦衍生物3,7-二乙酰基-1,3,7-三氮杂-5-磷酸双环[3.3.1]壬烷-5-氧化物（DAPTA = O），以及基于DAPTA = O配体的金属配合物的第一个实例，即[铜^II（μ-CH ₃ COO）₂（κ ø -DAPTA = O）] ₂（1）和[钠（1κ OO' ;2κ ø -DAPTA = O）（甲醇）] ₂（BPH ₄）₂（2）。的催化活性1在亨利反应中进行了测试，并且有氧2,2,6,6-四甲基哌啶-1-氧基（TEMPO）介导的苯甲醇氧化。还使用3,5-二叔丁基邻苯二酚作为底物，对化合物 1作为儿茶酚氧化酶的模型系统进行了评估。动力学数据符合Michaelis-Menten方程，并能够获得催化反应的速率常数。该速率常数是使用双核Cu ^II配合物获得的该底物的最高速率常数。DFT计算放弃了基体的桥接模式结合类型，并提出了混合价Cu ^II / Cu ^I 络合物中间体，其中自旋电子密度主要集中在一个铜原子和一个有机配体上。