Ligand Effects in Bimetallic High Oxidation State Palladium Systems
- 2 November 2010
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 49 (23), 11249-11253
- https://doi.org/10.1021/ic1020912
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.This publication has 31 references indexed in Scilit:
- On the Mechanism of Palladium-Catalyzed Aromatic C−H OxidationJournal of the American Chemical Society, 2010
- Bimetallic Reductive Elimination from Dinuclear Pd(III) ComplexesJournal of the American Chemical Society, 2010
- Palladium-Catalyzed Ligand-Directed C−H Functionalization ReactionsChemical Reviews, 2010
- Bimetallic Palladium Catalysis: Direct Observation of Pd(III)−Pd(III) IntermediatesJournal of the American Chemical Society, 2009
- Organopalladium and platinum chemistry in oxidising milieu as models for organic synthesis involving the higher oxidation states of palladiumDalton Transactions, 2009
- A bonding model for gold(I) carbene complexesNature Chemistry, 2009
- Synthetic and Mechanistic Studies of Pd-Catalyzed C−H Arylation with Diaryliodonium Salts: Evidence for a Bimetallic High Oxidation State Pd IntermediateJournal of the American Chemical Society, 2009
- Conformational Analysis of Olefin−Carbene Ruthenium Metathesis CatalystsOrganometallics, 2009
- Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent InteractionsJournal of Chemical Theory and Computation, 2006
- An Unbridged Platinum(III) Dimer with Added Chloro Ligands in Equatorial Sites, [Pt2Cl2(phpy)4] (Hphpy = phenylpyridine), Synthesized by an Oxidation with Aurous ComplexChemistry Letters, 2004