The role of the 5f orbitals in bonding, aromaticity, and reactivity of planar lsocyclic and heterocyclic uranium clusters
| dc.contributor.author | Tsipis, A. C. | en |
| dc.contributor.author | Kefalidis, C. E. | en |
| dc.contributor.author | Tsipis, C. A. | en |
| dc.date.accessioned | 2015-11-24T16:51:09Z | |
| dc.date.available | 2015-11-24T16:51:09Z | |
| dc.identifier.issn | 0002-7863 | - |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/9697 | |
| dc.rights | Default Licence | - |
| dc.subject | density-functional calculations | en |
| dc.subject | electron-transfer reactions | en |
| dc.subject | chemical-shifts nics | en |
| dc.subject | tetracoordinate carbon | en |
| dc.subject | actinide complexes | en |
| dc.subject | infrared-spectra | en |
| dc.subject | solid neon | en |
| dc.subject | theoretical investigations | en |
| dc.subject | relativistic dft | en |
| dc.subject | cuo(ng)(n) ng | en |
| dc.title | The role of the 5f orbitals in bonding, aromaticity, and reactivity of planar lsocyclic and heterocyclic uranium clusters | en |
| heal.abstract | The molecular and electronic structures, stabilities, bonding features and magnetic properties of prototypical planar isocyclic cyclo-U(n)X(n) (n = 3, 4; X = O, NH) and heterocyclic cyclo-U(n)(mu(2)-X)(n) (n = 3, 4; X = C, CH, NH) clusters as well as the E@[c-U(4)(mu(2)-C)(4)], (E = H(+), C, Si, Ge) and U@[c-U(5)(mu(2)-C)(5)] molecules including a planar tetracoordinate element E (ptE) and pentacoordinate U (ppU) at the ring centers, respectively, have been thoroughly investigated by means of electronic structure calculation methods at the DFT level. It was shown that 5f orbitals play a key role in the bonding of these f-block metal systems significantly contributing to the cyclic electron delocalization and the associated magnetic diatropic (magnetic aromaticity) response. The aromaticity of the perfectly planar cyclo-U(n)X(n) (n = 3, 4; X = O, NH), cyclo-U(n) (mu(2)-X)(n) (n = 3, 4; X = C, CH, NH), E @ [c-U(4)(mu(2)-C)(4)], (E = H(+), C, Si, Ge) and U @ [c-U(5)(mu(2)-C)(5)] clusters was verified by an efficient and simple criterion in probing the aromaticity/antiaromaticity of a molecule, that of the nucleus-independent chemical shift, NICS(0), NICS(1), NICS(zz)(0) and the most refined NICS(zz)(1) index in conjunction with the NICS scan profiles. Natural bond orbital analyses provided a clear picture of the bonding pattern in the planar isocyclic and heterocyclic uranium clusters and revealed the features that stabilize the ptE's inside the six- and eight-member uranacycle rings. The ptE's benefit from a considerable electron transfer from the surrounding uranium atoms in the E@[c-U(4)(mu(2)-C)(4)], (E = H(+), C, Si, Ge) and U@[c-U(5)(mu(2)-C)(5)]clusters justifying the high occupancy of the np orbitals of the central atom E. | en |
| heal.access | campus | - |
| heal.fullTextAvailability | TRUE | - |
| heal.identifier.primary | Doi 10.1021/Ja802344z | - |
| heal.identifier.secondary | <Go to ISI>://000257507400047 | - |
| heal.identifier.secondary | http://pubs.acs.org/doi/pdfplus/10.1021/ja802344z | - |
| heal.journalName | J Am Chem Soc | en |
| heal.journalType | peer reviewed | - |
| heal.language | en | - |
| heal.publicationDate | 2008 | - |
| heal.recordProvider | Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας | el |
| heal.type | journalArticle | - |
| heal.type.el | Άρθρο Περιοδικού | el |
| heal.type.en | Journal article | en |
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