Kumar Rakesh, Keshri Rahul, Prodhan Koushik, Shaikh Kanchan, Draksharapu Apparao
Southern Laboratories-208A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur - 208016, India.
Dalton Trans. 2023 Oct 31;52(42):15412-15419. doi: 10.1039/d3dt00761h.
Through dioxygen activation, a tetranuclear Mn(II,III,III,II) diamond core, Mn(HPTP*)(μ-O)(HO) (1) complex, has been synthesised using a suitably designed septadentate ligand framework (HPTP*H = 1,3-bis(bis((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amino)propan-2-ol). The newly prepared complex 1 was characterised using multiple spectroscopic techniques and X-ray crystallography. 1 exhibits excellent catalytic oxidation reactivity for the model substrates, namely, 3,5-di--butylcatechol (3,5-DTBC) and 2-aminophenol, efficiently mimicking the enzymes catechol oxidase and phenoxazinone synthase, respectively. Remarkably, we employed aerial oxygen to catalyze the oxidation of these model substrates, 3,5-DTBC and 2-aminophenol, with turnover numbers of 835 and 14, respectively. A tetranuclear Mn-diamond core complex that mimics both catechol oxidase and phenoxazinone synthase could pave the way for further research into its potential as a multi-enzymatic functional mimic.
通过双氧活化，利用精心设计的七齿配体框架（HPTP*H = 1,3-双（双（（4-甲氧基-3,5-二甲基吡啶-2-基）甲基）氨基）丙-2-醇）合成了四核Mn（II,III,III,II）金刚石核配合物Mn(HPTP*)(μ-O)(HO)（1）。使用多种光谱技术和X射线晶体学对新制备的配合物1进行了表征。配合物1对模型底物3,5-二叔丁基邻苯二酚（3,5-DTBC）和2-氨基苯酚表现出优异的催化氧化反应活性，分别有效模拟了儿茶酚氧化酶和吩恶嗪酮合酶。值得注意的是，我们利用空气中的氧气催化这些模型底物3,5-DTBC和2-氨基苯酚的氧化反应，周转数分别为835和14。一种同时模拟儿茶酚氧化酶和吩恶嗪酮合酶的四核锰金刚石核配合物，可能为进一步研究其作为多功能酶功能模拟物的潜力铺平道路。
