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Ligand effects in bimetallic high oxidation state palladium systems

Journal Article


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.

UOW Authors


  •   Ariafard, Alireza (external author)
  •   Hyland, Christopher
  •   Canty, Allan J. (external author)
  •   Sharma, Manab (external author)
  •   Brookes, Nigel J. (external author)
  •   Yates, Brian F. (external author)

Publication Date


  • 2010

Citation


  • Ariafard, A., Hyland, C. J. T., Canty, A. J., Sharma, M., Brookes, N. J. & Yates, B. F. (2010). Ligand effects in bimetallic high oxidation state palladium systems. Inorganic Chemistry: including bioinorganic chemistry, 49 (23), 11249-11253.

Scopus Eid


  • 2-s2.0-78650239417

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/2323

Number Of Pages


  • 4

Start Page


  • 11249

End Page


  • 11253

Volume


  • 49

Issue


  • 23

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.

UOW Authors


  •   Ariafard, Alireza (external author)
  •   Hyland, Christopher
  •   Canty, Allan J. (external author)
  •   Sharma, Manab (external author)
  •   Brookes, Nigel J. (external author)
  •   Yates, Brian F. (external author)

Publication Date


  • 2010

Citation


  • Ariafard, A., Hyland, C. J. T., Canty, A. J., Sharma, M., Brookes, N. J. & Yates, B. F. (2010). Ligand effects in bimetallic high oxidation state palladium systems. Inorganic Chemistry: including bioinorganic chemistry, 49 (23), 11249-11253.

Scopus Eid


  • 2-s2.0-78650239417

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/2323

Number Of Pages


  • 4

Start Page


  • 11249

End Page


  • 11253

Volume


  • 49

Issue


  • 23