Bibliographic Details
| Title: |
Ligand Effects in Bimetallic High Oxidation State Palladium Systems. |
| Authors: |
Alireza Ariafard1,2, Hyland, Christopher J. T.2,3, Allan J. Canty2 allan.canty@utas.edu.au, Manab Sharma2, Brookes, Nigel J.2, Yates, Brian F.2 brian.yates@utas.edu.au |
| Source: |
Inorganic Chemistry. 12/6/2010, Vol. 49 Issue 23, p11249-11253. 5p. |
| Subject Terms: |
*LIGANDS (Chemistry), *OXIDATION, *PALLADIUM, *DENSITY functionals, *DISSOCIATION (Chemistry), *BASIC proteins, *POLARITY (Chemistry) |
| Abstract: |
Ligand effects in bimetallic high oxidation state systems containing a X-Pd-Pd-Y framework have been explored with density functional theory (DFT). The ligand X has a strong effect on the dissociation reaction of Y to form [X-Pd-Pd]+ + Y-. In the model system examined where Y is a weak σ-donor ligand and a good leaving group, we find that dissociation of Y is facilitated by greater σ-donor character of X relative to Y. We find that there is a linear correlation of the Pd-Y and Pd-Pd bond lengths with Pd-Y bond dissociation energy, and with the σ-donating ability of X. These results can be explained by the observation that the Pd dz2 population in the PdY fragment increases as the donor ability of X increases. In these systems, the PdIII-PdIII arrangement is favored when X is a weak σ-donor ligand, while the PdIV-PdII arrangement is favored when X is a strong σ-donor ligand. Finally, we demonstrate that ligand exchange to form a bimetallic cationic species in which each Pd is six-coordinate should be feasible in a high polarity solvent. [ABSTRACT FROM AUTHOR] |
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