The nucleophile can be oxidized by electrophilic intermediates generated on electrocatalysts under the oxidation potential,and nucleophile oxidation reaction(NOR)has attracted extensive attention in the fields of coup...The nucleophile can be oxidized by electrophilic intermediates generated on electrocatalysts under the oxidation potential,and nucleophile oxidation reaction(NOR)has attracted extensive attention in the fields of coupling hydrogen production and organic electrosynthesis.Given that NOR involves electrocatalysis and organic chemistry,the development of this cross-disciplinary field requires a close multi-disciplinary collaboration.Although numerous studies about NOR have sprung up,researchers cannot agree on the NOR mechanism,let alone on utilizing the NOR mechanism.Hence,critically reviewing past works is crucial to establishing a unified conclusion for the NOR mechanism.This review concludes the current progress of NOR and proposes a unified NOR mechanism,which offers guidance and inspiration to subsequent studies of NOR.Firstly,we summarize the adjustable NOR systems,including multiple high-efficiency NOR electrocatalysts and numerous substrate/product systems.Secondly,we discuss the NOR mechanism involving an electrochemical step and a spontaneous non-electrochemical process,and propose the connection between the non-electrochemical process and the nucleophile oxidation pathway.Thirdly,we highlight the design principle of highly effective NOR electrocatalysts based on the NOR mechanism.Finally,several critical issues for the future development of NOR are presented.展开更多
A peroxonickel(III)complex bearing the Me6-trien ligand,an open-chain analogue of the macrocyclic 12-TMC ligand,was synthesized and characterized by several physical methods,such as UV-vis,resonance Raman,ESI-MS and E...A peroxonickel(III)complex bearing the Me6-trien ligand,an open-chain analogue of the macrocyclic 12-TMC ligand,was synthesized and characterized by several physical methods,such as UV-vis,resonance Raman,ESI-MS and EPR.Density functional theory calculations provide geometric and electronic configurations of peroxonickel(III)complexes.The reactivity of the peroxonickel(III)intermediate was examined in oxidative nucleophilic reactions(e.g.,aldehyde deformylation).By comparing the reactivities of the open-chain and macrocyclic peroxonickel(III)complexes under identical reaction conditions,we were able to demonstrate that the open-chain peroxonickel(III)complex is much more reactive than the macrocyclic analogue in aldehyde deformylation.This result provides intriguing aspects of the reactivity differences for open-chain vs.macrocyclic systems of metal complexes.展开更多
基金supported by the National Key R&D Program of China(2023YFA1507400)the National Natural Science Foundation of China(U24A20498,21573066,21825201,22402056,U1932212)+3 种基金the Fundamental Research Funds for the Central Universities(531118010127)the Provincial Natural Science Foundation of Hunan(2020JJ5045,2025JJ40013)the Changsha Natural Science Foundation(kq2402052)the Hunan Provincial Basic Research Project for Young Students(2024JJ10030)。
文摘The nucleophile can be oxidized by electrophilic intermediates generated on electrocatalysts under the oxidation potential,and nucleophile oxidation reaction(NOR)has attracted extensive attention in the fields of coupling hydrogen production and organic electrosynthesis.Given that NOR involves electrocatalysis and organic chemistry,the development of this cross-disciplinary field requires a close multi-disciplinary collaboration.Although numerous studies about NOR have sprung up,researchers cannot agree on the NOR mechanism,let alone on utilizing the NOR mechanism.Hence,critically reviewing past works is crucial to establishing a unified conclusion for the NOR mechanism.This review concludes the current progress of NOR and proposes a unified NOR mechanism,which offers guidance and inspiration to subsequent studies of NOR.Firstly,we summarize the adjustable NOR systems,including multiple high-efficiency NOR electrocatalysts and numerous substrate/product systems.Secondly,we discuss the NOR mechanism involving an electrochemical step and a spontaneous non-electrochemical process,and propose the connection between the non-electrochemical process and the nucleophile oxidation pathway.Thirdly,we highlight the design principle of highly effective NOR electrocatalysts based on the NOR mechanism.Finally,several critical issues for the future development of NOR are presented.
基金financial support from the NRF(2017R1A2B4005441 and 2018R1A5A1025511)the Ministry of Science,ICT and Future Planning(CGRC 2016M3D3A01913243)of Korea.T.O.acknowledges the support of“Strategic Young Researcher Overseas Visits Program for Accelerating Brain Circulation”.
文摘A peroxonickel(III)complex bearing the Me6-trien ligand,an open-chain analogue of the macrocyclic 12-TMC ligand,was synthesized and characterized by several physical methods,such as UV-vis,resonance Raman,ESI-MS and EPR.Density functional theory calculations provide geometric and electronic configurations of peroxonickel(III)complexes.The reactivity of the peroxonickel(III)intermediate was examined in oxidative nucleophilic reactions(e.g.,aldehyde deformylation).By comparing the reactivities of the open-chain and macrocyclic peroxonickel(III)complexes under identical reaction conditions,we were able to demonstrate that the open-chain peroxonickel(III)complex is much more reactive than the macrocyclic analogue in aldehyde deformylation.This result provides intriguing aspects of the reactivity differences for open-chain vs.macrocyclic systems of metal complexes.
