Transition state symmetries and theoretical activation enthalpies for chloride exchange at planar [PdCl4](2-)
UNSPECIFIED (1996) Transition state symmetries and theoretical activation enthalpies for chloride exchange at planar [PdCl4](2-). CHEMICAL PHYSICS LETTERS, 261 (1-2). pp. 45-50. ISSN 0009-2614Full text not available from this repository.
Density functional theory is applied to associatively activated and dissociative chloride exchange on planar [PdCl4](2-). It is shown generally that the highest possible transition state symmetry for associative activation is C-2v. However, for [PdCl5](3-), the rigorously trigonal bipyramidal (D-3h) geometry has virtually the same energy and geometry. Enthalpic corrections have little effect on the DFT energy barriers although DFT alone predicts dissociation to be preferred due to the more favourable electrostatic interactions. Inclusion of solvation enthalpies establishes associative activation as the lower energy pathway in agreement with experimental assignments for related processes.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry
Q Science > QC Physics
|Journal or Publication Title:||CHEMICAL PHYSICS LETTERS|
|Publisher:||ELSEVIER SCIENCE BV|
|Date:||11 October 1996|
|Number of Pages:||6|
|Page Range:||pp. 45-50|
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