DC Field | Value | Language |
---|---|---|
dc.contributor.author | Oh, Changjin | ko |
dc.contributor.author | Siewe, Joelle | ko |
dc.contributor.author | Nguyen, Thao T. | ko |
dc.contributor.author | Kawamura, Airi | ko |
dc.contributor.author | Flores, Marco | ko |
dc.contributor.author | Groy, Thomas L. | ko |
dc.contributor.author | Anderson, John S. | ko |
dc.contributor.author | Trovitch, Ryan J. | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.date.accessioned | 2020-12-23T06:10:04Z | - |
dc.date.available | 2020-12-23T06:10:04Z | - |
dc.date.created | 2020-12-14 | - |
dc.date.created | 2020-12-14 | - |
dc.date.issued | 2020-11 | - |
dc.identifier.citation | DALTON TRANSACTIONS, v.49, no.41, pp.14463 - 14474 | - |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.uri | http://hdl.handle.net/10203/278945 | - |
dc.description.abstract | The electronic structure of a dimeric manganese hydride catalyst supported by beta-diketiminate ligands, [(2,6-iPr2PhBDI)Mn(mu-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 J(0) value of -10.9 cm(-1) confirmed that the ground state involves antiferromagnetic coupling between high spin Mn(II)-d(5) centres. The effect of steric bulk on the bond order was examined via a model study with the least sterically-demanding version of the beta-diketiminate ligand and was found to be negligible. Mixing between metal- and beta-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(mu-OH)](2), provides experimental support for these assessments. | - |
dc.language | English | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | The Electronic Structure of a Beta-Diketiminate Manganese Hydride Dimer | - |
dc.type | Article | - |
dc.identifier.wosid | 000587719100017 | - |
dc.identifier.scopusid | 2-s2.0-85094931049 | - |
dc.type.rims | ART | - |
dc.citation.volume | 49 | - |
dc.citation.issue | 41 | - |
dc.citation.beginningpage | 14463 | - |
dc.citation.endingpage | 14474 | - |
dc.citation.publicationname | DALTON TRANSACTIONS | - |
dc.identifier.doi | 10.1039/d0dt02842h | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Siewe, Joelle | - |
dc.contributor.nonIdAuthor | Nguyen, Thao T. | - |
dc.contributor.nonIdAuthor | Kawamura, Airi | - |
dc.contributor.nonIdAuthor | Flores, Marco | - |
dc.contributor.nonIdAuthor | Groy, Thomas L. | - |
dc.contributor.nonIdAuthor | Anderson, John S. | - |
dc.contributor.nonIdAuthor | Trovitch, Ryan J. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | MOLECULAR CALCULATIONS | - |
dc.subject.keywordPlus | SPIN-RESONANCE | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | 2-COORDINATE | - |
dc.subject.keywordPlus | REDUCTION | - |
dc.subject.keywordPlus | CHEMISTRY | - |
dc.subject.keywordPlus | ATOMS | - |
dc.subject.keywordPlus | SCOPE | - |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.