Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Corona Teresa; Pfaff Florian F.; Acuna-Pares Ferran; Draksharapu Apparao; Whiteoak Christopher J.; Martin-Diaconescu Vlad; Lloret-Fillol Julio; Browne Wesley R.; Ray Kallol; Company Anna

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Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

机译：双（酰胺）镍（II）配合物与间氯过苯甲酸的反应活性：潜在氧化物种的形成。

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Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a Ni-II precursor bearing a macrocyclic bis(amidate) ligand with meta-chloroperbenzoic acid (HmCPBA). This compound is only detectable at temperatures below 250 K and is much more reactive toward organic substrates (i.e., C - H bonds, C=C bonds, and sulfides) than previously reported well-defined nickel-oxygen species. Remarkably, this species is formed by heterolytic O-O bond cleavage of a Ni-HmCPBA precursor, which is concluded from experimental and computational data. On the basis of spectroscopy and DFT calculations, this reactive species is proposed to be a Ni-III-oxyl compound.

机译：在本文中，我们报道了形成高反应性镍-氧物种的过程，该物种已被带有大环双（氨基甲酸酯）配体的Ni-II前体与间氯过苯甲酸（HmCPBA）反应捕获。该化合物仅在低于250 K的温度下才可检测到，并且比以前报道的定义明确的镍氧物种对有机底物（即C-H键，C = C键和硫化物）的反应性强得多。值得注意的是，该物种是由Ni-HmCPBA前体的杂合O-O键裂解形成的，该裂解由实验和计算数据得出。根据光谱学和DFT计算，该反应性物质被提议为Ni-III-氧基化合物。

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来源
《Chemistry: A European journal》 |2015年第42期|共10页
作者
Corona Teresa; Pfaff Florian F.; Acuna-Pares Ferran; Draksharapu Apparao; Whiteoak Christopher J.; Martin-Diaconescu Vlad; Lloret-Fillol Julio; Browne Wesley R.; Ray Kallol; Company Anna;
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正文语种 eng
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high-valent metal species; nickel; oxidation; reactive intermediates; redox chemistry;

机译：高价金属;镍;氧化;反应中间体;氧化还原化学;

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1. Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species [J] . Corona Teresa, Pfaff Florian F., Acuna-Pares Ferran, Chemistry: A European journal . 2015,第42期

机译：双（酰胺）镍（II）配合物与间氯过苯甲酸的反应活性：潜在氧化物种的形成。
2. Acid-Base Properties of Bis(hydrazinocarbonylmethyl) Sulfoxide and Its Complex Formation with Copper(II) and Nickel(II) [J] . V. V. Neklyudov, G. A. Boos, S. G. Fattakhov Russian Journal of General Chemistry . 2014,第3期

机译：双（肼基羰基甲基）亚砜的酸碱性质及其与铜（II）和镍（II）的络合物形成
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机译：N，N-二甲基甲酰胺（DMF）中四（N）烷基化的环烷酰胺与镍（II）络合形成的动力学和机理：Ni（DMF）（6）（2+）物种的反应性和溶剂交换的比较研究和Ni（DMF）（5）Cl +
4. Reactive Oxygen Species Influence Biofilm Formation of Acidophilic Mineral-Oxidizing Bacteria on Pyrite [C] . Soren Bellenberg, Dieu Huynh Ngoc, Laura Castro, International Biohydrometallurgy Symposium . 2015

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5. I. Synthesis, reactivity, and structural studies of rhodium(III) and rhodium(II) complexes of novel bis(oxazoline) pincer ligands. II. Synthesis and reactivity of novel rhenium methylidene complexes. [D] . Krumper, Jennifer. 2003

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7. Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species [O] . Corona Prieto, Teresa, Pfaff, Florian F., Acuña-Parés, Ferran, 2015

机译：双（酰胺）镍（II）配合物与间氯过苯甲酸的反应活性：潜在氧化物种的形成。
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Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

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