Yi-Rong Hsiang, Naorem Jemes Meitei, Gifta Evangeline Henry, Sodio C. N. Hsu, Ya-Fan Lin
{"title":"Mechanistic insights into nitric oxide generation from nitrite via O-atom transfer in the unsymmetrical ꞵ-diketiminato copper(II) nitrite complex","authors":"Yi-Rong Hsiang, Naorem Jemes Meitei, Gifta Evangeline Henry, Sodio C. N. Hsu, Ya-Fan Lin","doi":"10.1039/d4dt02359e","DOIUrl":null,"url":null,"abstract":"In this study, we employed DFT calculations to elucidate the mechanism of NO generation from nitrite via PPh<small><sub>3</sub></small>-induced oxygen atom transfer (OAT) in the unsymmetrical ß-diketiminato copper(II), LCu<small><sup>II</sup></small>ONO. We discovered that the OAT process involves the cooperation of the two PPh<small><sub>3</sub></small> and follows the mechanism distinct from that of the symmetrical ß-diketiminato analogue. The ΔG<small><sup>‡</sup></small> value, calculated to be 34.8 kcal/mol, closely matches experimental data. The finding is further supported by analyzing the OAT product yields with varying equivalents of PPh<small><sub>3</sub></small>. The penta-coordinated species <strong>5a</strong>, with PPh<small><sub>3</sub></small> occupying the axial site, forms in the final stage of the OAT process. The isomerization of <strong>5a</strong> and the decoordination of the hemilabile pyridyl arm synergistically reduce Cu(II) to Cu(I), facilitating NO-releasing from the Cu(I) centre. These computational results provide valuable insights for the ligand design of PPh<small><sub>3</sub></small>-induced OAT reactions to produce NO in Cu(II) nitrite systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4dt02359e","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
In this study, we employed DFT calculations to elucidate the mechanism of NO generation from nitrite via PPh3-induced oxygen atom transfer (OAT) in the unsymmetrical ß-diketiminato copper(II), LCuIIONO. We discovered that the OAT process involves the cooperation of the two PPh3 and follows the mechanism distinct from that of the symmetrical ß-diketiminato analogue. The ΔG‡ value, calculated to be 34.8 kcal/mol, closely matches experimental data. The finding is further supported by analyzing the OAT product yields with varying equivalents of PPh3. The penta-coordinated species 5a, with PPh3 occupying the axial site, forms in the final stage of the OAT process. The isomerization of 5a and the decoordination of the hemilabile pyridyl arm synergistically reduce Cu(II) to Cu(I), facilitating NO-releasing from the Cu(I) centre. These computational results provide valuable insights for the ligand design of PPh3-induced OAT reactions to produce NO in Cu(II) nitrite systems.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.