Deciphering the bonding mode of the trihalide ligands in a series of halogen carrier homo- and hetero-trihalide Cu(II) Schiff base complexes

 
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2008 (EN)
Deciphering the bonding mode of the trihalide ligands in a series of halogen carrier homo- and hetero-trihalide Cu(II) Schiff base complexes (EN)

Tsipis, A. C. (EN)

Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας (EL)
Tsipis, A. C. (EN)

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)

trihalides (EN)

Πανεπιστήμιο Ιωαννίνων (EL)
University of Ioannina (EN)

Polyhedron (EN)

2008

<Go to ISI>://000253191100037



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