Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2022-02-22T16:31:13Z | - |
dc.date.available | 2022-02-22T16:31:13Z | - |
dc.date.issued | 2021 | * |
dc.identifier.issn | 0253-2964 | * |
dc.identifier.issn | 1229-5949 | * |
dc.identifier.other | OAK-30692 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/260654 | - |
dc.description.abstract | This account article focuses on deuterium kinetic isotope effects (KIEs) used as criterions to elucidate redox mechanisms including proton-, hydrogen- and hydride-transfer reactions. Hydrogen atom transfer (HAT) is composed of two elementary steps: electron transfer (ET) and proton transfer (PT), while hydride transfer is composed of three elementary steps: ET, PT, and ET. Large tunneling effects are often observed for proton-coupled electron-transfer (PCET) reactions of metal-oxygen complexes in which ET occurs to the metal center and PT occurs simultaneously to the ligand, exhibiting large KIEs. Whether HAT proceeds via sequential ET/PT, PT/ET, or concerted PCET (cPCET) depending on the redox properties of hydrogen donors and acceptors to exhibit different KIEs. Whether hydride transfer also proceeds via sequential ET/PT/ET, PT/ET/ET, or cPCET/ET depending on the redox properties of hydride donors and acceptors to exhibit different KIEs. Temperature dependence of KIEs for aldehyde deformylation reactions has enabled to distinguish two reaction pathways: one is a HAT and the other is a nucleophilic addition. The change of the mechanism from cPCET to sequential ET/PT is made possible by binding acids to the hydrogen and hydride acceptors when no KIE is observed. Inverse KIEs are also discussed for acid (or deuteron)-promoted ET reactions. | * |
dc.language | English | * |
dc.publisher | WILEY-V C H VERLAG GMBH | * |
dc.subject | acid-promoted electron transfer | * |
dc.subject | deuterium kinetic isotope effect | * |
dc.subject | inverse kinetic isotope effect | * |
dc.subject | proton-coupled electron transfer | * |
dc.subject | tunneling effect | * |
dc.title | Deuterium kinetic isotope effects as redox mechanistic criterions | * |
dc.type | Article | * |
dc.relation.issue | 12 | * |
dc.relation.volume | 42 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 1558 | * |
dc.relation.lastpage | 1568 | * |
dc.relation.journaltitle | BULLETIN OF THE KOREAN CHEMICAL SOCIETY | * |
dc.identifier.doi | 10.1002/bkcs.12417 | * |
dc.identifier.wosid | WOS:000715872500001 | * |
dc.identifier.scopusid | 2-s2.0-85118877724 | * |
dc.author.google | Fukuzumi, Shunichi | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Nam, Wonwoo | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240426135715 | * |