The electronic structure of a β-diketiminate manganese hydride dimer
DC Field | Value | Language |
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dc.contributor.author | Changjin Oh | - |
dc.contributor.author | Joëlle Siewe | - |
dc.contributor.author | Thao T. Nguyen | - |
dc.contributor.author | Airi Kawamura | - |
dc.contributor.author | Marco Flores | - |
dc.contributor.author | Thomas L. Groy | - |
dc.contributor.author | John S. Anderson | - |
dc.contributor.author | Ryan J. Trovitch | - |
dc.contributor.author | Mu-Hyun Baik | - |
dc.date.accessioned | 2020-12-22T02:24:12Z | - |
dc.date.accessioned | 2020-12-22T02:24:12Z | - |
dc.date.available | 2020-12-22T02:24:12Z | - |
dc.date.available | 2020-12-22T02:24:12Z | - |
dc.date.created | 2020-11-18 | - |
dc.date.issued | 2020-11 | - |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.uri | https://pr.ibs.re.kr/handle/8788114/7559 | - |
dc.description.abstract | © The Royal Society of Chemistry. The electronic structure of a dimeric manganese hydride catalyst supported by β-diketiminate ligands, [(2,6-iPr2PhBDI)Mn(μ-H)]2, was investigated with density functional theory. A triple bond between the manganese centres was anticipated from simple electron-counting rules; however, calculations revealed Mn-Mn Mayer bond orders of 0.21 and 0.27 for the ferromagnetically-coupled and antiferromagnetically-coupled extremes, respectively. In accordance with experimentally determined Heisenberg exchange coupling constants of -15 ± 0.1 cm-1 (SQUID) and -10.2 ± 0.7 cm-1 (EPR), the calculated J0 value of -10.9 cm-1 confirmed that the ground state involves antiferromagnetic coupling between high spin Mn(ii)-d5 centres. The effect of steric bulk on the bond order was examined via a model study with the least sterically-demanding version of the β-diketiminate ligand and was found to be negligible. Mixing between metal- and β-diketiminate-based orbitals was found to be responsible for the absence of a metal-metal multiple bond. The bridging hydrides give rise to a relatively close positioning of the metal centres, while bridging atoms possessing 2p orbitals result in longer Mn-Mn distances and more stable dimers. The synthesis and characterization of the bridging hydroxide variant, [(2,6-iPr2PhBDI)Mn(μ-OH)]2, provides experimental support for these assessments. This journal i | - |
dc.language | 영어 | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | The electronic structure of a β-diketiminate manganese hydride dimer | - |
dc.type | Article | - |
dc.type.rims | ART | - |
dc.identifier.wosid | 000587719100017 | - |
dc.identifier.scopusid | 2-s2.0-85094931049 | - |
dc.identifier.rimsid | 73683 | - |
dc.contributor.affiliatedAuthor | Changjin Oh | - |
dc.contributor.affiliatedAuthor | Joëlle Siewe | - |
dc.contributor.affiliatedAuthor | Mu-Hyun Baik | - |
dc.identifier.doi | 10.1039/d0dt02842h | - |
dc.identifier.bibliographicCitation | DALTON TRANSACTIONS, v.49, no.41, pp.14463 - 14474 | - |
dc.relation.isPartOf | DALTON TRANSACTIONS | - |
dc.citation.title | DALTON TRANSACTIONS | - |
dc.citation.volume | 49 | - |
dc.citation.number | 41 | - |
dc.citation.startPage | 14463 | - |
dc.citation.endPage | 14474 | - |
dc.description.journalClass | 1 | - |
dc.description.journalClass | 1 | - |
dc.description.isOpenAccess | N | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Inorganic & Nuclear | - |
dc.subject.keywordPlus | EFFECTIVE CORE POTENTIALS | - |
dc.subject.keywordPlus | MOLECULAR CALCULATIONS | - |
dc.subject.keywordPlus | SPIN-RESONANCE | - |
dc.subject.keywordPlus | METAL ATOMS | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | 2-COORDINATE | - |
dc.subject.keywordPlus | REDUCTION | - |
dc.subject.keywordPlus | CHEMISTRY | - |
dc.subject.keywordPlus | SCOPE | - |