Peroxocobalt(III) species activates nitriles via a superoxocobalt(II) diradical state

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Peroxocobalt(III) species activates nitriles via a superoxocobalt(II) diradical state

机译：过氧钴（III）物种通过超氧基钴（II）Daradical状态激活腈

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The dioxygenation of nitriles by [Co-III(TBDAP)(O-2)](+) (TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane) is investigated using DFT-calculations. The mechanism proposed previously based on experimental observations, which invoked an outer-sphere cycloaddition, was found to be unreasonable. Instead, calculations suggest that an inner-sphere mechanism involving the cleavage of one of the Co-O bonds assisted by substrate uptake is much more likely. The reactively competent species is a triplet consisting of a Co(II)-superoxo functionality, which can undergo O-C bond formation and O-O bond cleavage traversing low energy transition states. The role of the structurally rigid TBDAP ligand is to prevent the participation of the pyridyl ligand in the delocalization of the unpaired electron density.

机译：[Co-III（TBDAP）（O-2）]（+）（TBDAP = N，N-二叔丁基-2,11- diaza [3.3]（2,6） - 吡啶烷烷腈的二氧化使用DFT计算调查。发现先前基于实验观察的机制，该机制被认为是不合理的。相反，计算表明，涉及碱吸收辅助的一个CO-O键的切割的内球机构更可能。反应性竞争性物种是由CO（II）-Superoxo官能团组成的三重态，其可以经历O-C键形成和O-O键切割穿过低能量过渡状态。结构刚性TBDAP配体的作用是为了防止吡啶基配体参与未配对的电子密度的分层。

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《Dalton transactions: An international journal of inorganic chemistry》 |2020年第9期|共8页
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中图分类化学;无机化学;
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1. Peroxocobalt(III) species activates nitriles via a superoxocobalt(II) diradical state [J] . Dalton transactions: An international journal of inorganic chemistry . 2020,第9期

机译：过氧钴（III）物种通过超氧基钴（II）Daradical状态激活腈
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3. Co(III) complexes with coordinated carboxamido nitrogens and thiolato sulfurs as models for co-containing nitrile hydratase and their conversion to the corresponding sulfinato species [J] . Tyler LA., Olmstead MM., Mascharak PK., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2000,第2期

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4. Light propagation properties of Si waveguides after removing III#x2013;V layer on a III#x2013;V/SOI wafer fabricated by plasma activated bonding [C] . Suzuki Junichi, Hayashi Yusuke, Kuno Yuki, 2014 4th IEEE International Workshop on Low Temperature Bonding for 3D Integration . 2014

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5. Developing artificial proteases and nucleases: Catalytic hydrolysis of unactivated amides, nitriles and phosphates. Part~I. Hydrolysis of phosphate esters promoted by cobalt(III) complexes. Part~II. Hydration of nitriles catalyzed by cobalt(III) complexes. Part~III. Hydrolysis of amides promoted by cobalt(III) complexes. [D] . Kim, Jung Hee. 1992

机译：开发人造蛋白酶和核酸酶：催化水解未活化的酰胺，腈和磷酸盐。第一部分钴（III）配合物促进的磷酸酯的水解。第二部分钴（III）配合物催化的腈水合。第三部分钴（III）配合物促进的酰胺水解。
6. Characterization of a Heterobimetallic Nonheme Fe(III)-O-Cr(III) Species Formed by O2 Activation [O] . Ang Zhou, Scott T. Kleespies, Katherine M. Van Heuvelen, -1

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机译：通过O2活化形成的异质非血液Fe（III）-O-Cr（III）物种的表征
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机译：医学昆虫学研究 - VII。东南亚伊蚊的亚属stegomyia。 II - 爱德华兹物种群。 III - W-albus物种组。（双翅目：蚊科）。 VIII：关于伊蚊（aedes Vittatus）的分类地位的说明（Deptera：蚊科（Culicidae））（美国昆虫研究所的贡献。第14卷，第1期）

Peroxocobalt(III) species activates nitriles via a superoxocobalt(II) diradical state

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