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Ligand effects in bimetallic high oxidation state palladium systems
journal contribution
posted on 2023-05-17, 04:42 authored by Alireza AriafardAlireza Ariafard, Hyland, CJT, Allan CantyAllan Canty, Sharma, M, Brookes, NJ, Brian YatesBrian YatesLigand 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 ó-donor ligand and a good leaving group, we find that dissociation of Y is facilitated by greater ó-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 ó-donating ability of X. These results can be explained by the observation that the Pd d(z(2)) population in the PdY fragment increases as the donor ability of X increases. In these systems, the Pd(III)-Pd(III) arrangement is favored when X is a weak ó-donor ligand, while the Pd(IV)-Pd(II) arrangement is favored when X is a strong ó-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.
History
Publication title
Inorganic ChemistryVolume
49Issue
23Pagination
11249-11253ISSN
0020-1669Department/School
School of Natural SciencesPublisher
Amer Chemical SocPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
Copyright © 2010 American Chemical SocietyRepository Status
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