Potential Energy Surfaces for Ligand Exchange Reactions of Square Planar Diamagnetic PtY2L2 Complexes:Hydrogen Bond (PtY2L2…L') versus Apical (Y2L2Pt…L') Interaction 


Vol. 27,  No. 9, pp. 1405-1417, Sep.  2006
10.5012/bkcs.2006.27.9.1405


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  Abstract

The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum (Pt22 : Y, L=Cl-, OH-, O2, N3) complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of (PtC4 + 2O) to [PtC3(2O) + Cl-] and [Pt(N32C2 + 2O] to [Pt(N32Cl(2O) + Cl-] were investigated in detail. For these two exchange reactions, the transition states ([Pt22…L']‡) correspond to complexes such as (PtC4…2O)‡ and [Pt(N32C2…2O]‡, respectively. In the transition state, ([PtC4…2O]‡ and [Pt(N32C2…2O]‡) have a kind of 6-membered (Pt-Cl…HOH…Cl) and (Pt-OH…Cl…HN) interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving Cl- and an entering 2O. Simultaneously, the entering 2O interacts with a leaving Cl-. No vertical one metal-ligand interactions ([Pt22 …L']‡) are found at the axial positions of the square planar (Pt22) complexes, which were formed via a vertically associative mechanism leading to 3h or 2v-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtC4(2On(n = 2,4)} into {PtC3(2O(n-2) + Cl-(2O2} and the binding energies {PtC4(2On(n = 1-5)} of PtC4 with water molecules are drawn.

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  Cite this article

[IEEE Style]

J. K. Park and B. G. Kim, "Potential Energy Surfaces for Ligand Exchange Reactions of Square Planar Diamagnetic PtY2L2 Complexes:Hydrogen Bond (PtY2L2…L') versus Apical (Y2L2Pt…L') Interaction," Bulletin of the Korean Chemical Society, vol. 27, no. 9, pp. 1405-1417, 2006. DOI: 10.5012/bkcs.2006.27.9.1405.

[ACM Style]

Jong Keun Park and Bong Gon Kim. 2006. Potential Energy Surfaces for Ligand Exchange Reactions of Square Planar Diamagnetic PtY2L2 Complexes:Hydrogen Bond (PtY2L2…L') versus Apical (Y2L2Pt…L') Interaction. Bulletin of the Korean Chemical Society, 27, 9, (2006), 1405-1417. DOI: 10.5012/bkcs.2006.27.9.1405.

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ISSN(Print) 0253-2964
ISSN(Online) 1229-5949