Deciphering the bonding mode of the trihalide ligands in a series of halogen carrier homo- and hetero-trihalide Cu(II) Schiff base complexes
| dc.contributor.author | Tsipis, A. C. | en |
| dc.contributor.author | Karipidis, P. A. | en |
| dc.date.accessioned | 2015-11-24T16:55:13Z | |
| dc.date.available | 2015-11-24T16:55:13Z | |
| dc.identifier.issn | 0277-5387 | - |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/10276 | |
| dc.rights | Default Licence | - |
| dc.subject | trihalides | en |
| dc.subject | schiff base | en |
| dc.subject | copper(ii) complexes | en |
| dc.subject | dft | en |
| dc.subject | bonding properties | en |
| dc.subject | quaternary ammonium polyhalides | en |
| dc.subject | benzyltrimethylammonium tribromide | en |
| dc.subject | crystal-structure | en |
| dc.subject | polyiodides | en |
| dc.subject | density | en |
| dc.subject | reagents | en |
| dc.subject | phenols | en |
| dc.title | Deciphering the bonding mode of the trihalide ligands in a series of halogen carrier homo- and hetero-trihalide Cu(II) Schiff base complexes | en |
| heal.abstract | Electronic structure calculation techniques (DFT) have been used to decipher the bonding of the trihalide ligands in a series of homo- and hetero-trihalide Cu(II) Schiff base complexes formulated as [Cu(RdienR)(X)(XY2)] (RdienR = Schiff base; R = furan, thiophene or pyrrol; X = Cl or Br; Y = Cl, Br or I). The association of the incoming Y-2 halogen molecule with one of the halide X ligands of the precursor [Cu(RdienR)(X)21 complexes alters their distorted trigonal bipyramidal stereochemistry which is transformed to a distorted square pyramidal geometry. The bonding mechanism between the halogen Y2 molecule and the halide X ligand was thoroughly explored by means of various electronic parameters and charge decomposition analysis techniques. The bond dissociation energy of the Cu-XY2 bond, BDECu-XY2, was estimated in the range of 61.9-68.4 kcal/mol, while the bond dissociation energy of the X-Y-2 bond, BDECu-XY2, was found in the range of 10.6-12.5 kcal/mol. It was found that the X...Y-2 interactions correspond to weak hyperconjugative donor-acceptor interactions between a non-bonding n(X) molecular orbital (donor orbital) localized on the coordinated halide X ligand and an antibonding sigma*(Y-Y) molecular orbital (acceptor orbital) localized on the Y-2 halogen molecule. The n(X) -> sigma*(Y-Y) donor-acceptor interactions are associated with a second-order perturbation stabilization energy, Delta E(2) of 34.5-52.5 kcal/mol. The loose association of the halogen molecules with the coordinated halide ligand renders the [Cu(RdienR)(X)(XY2)1 complexes good halogen carrier molecules. (C) 2007 Elsevier Ltd. All rights reserved. | en |
| heal.access | campus | - |
| heal.fullTextAvailability | TRUE | - |
| heal.identifier.primary | DOI 10.1016/j.poly.2007.09.005 | - |
| heal.identifier.secondary | <Go to ISI>://000253191100037 | - |
| heal.identifier.secondary | http://ac.els-cdn.com/S0277538707005530/1-s2.0-S0277538707005530-main.pdf?_tid=6329810ed613771478eaaa05bf2c6f2d&acdnat=1333113138_a4f505b2d31672c36c654243c0087eee | - |
| heal.journalName | Polyhedron | 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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