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Iodo-methyl ligand exchange reaction in platinum complexes: A density functional study |
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| Authors: | Tamás Kégl László Kollár |
| Institution: | a Research Group for Petrochemistry of the Hungarian Academy of Sciences, H-8200 Veszprém, Hungary b University of Pécs, Department of Inorganic Chemistry, H-7624 Pécs, P.O. Box 266, Hungary c Research Group for Chemical Sensors of the Hungarian Academy of Sciences, H-7624 Pécs, P.O. Box 266, Hungary |
| Abstract: | A theoretical investigation at the gradient-corrected density functional (BP86) level of theory on the iodo-methyl ligand exchange reaction in platinum-diphosphine complexes is discussed. The reaction consists of two elementary steps: the oxidative addition of methyl-iodide, and reductive elimination of ethane from the intermediate Pt(bdpp)(CH3)3I complex which is the rate determining step with a free energy of activation of 19.5 kcal/mol in acetonitrile phase. The oxidative addition step takes place with SN2 mechanism via a transition state with a collinear arrangement of the I-CH3-Pt moiety. |
| Keywords: | Platinum-diphosphine complexes Methyl-iodide SN2 reaction Density functional theory NBO analysis |
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