Electronic Structures of PdII Dimers
- 21 January 2010
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 49 (4), 1801-1810
- https://doi.org/10.1021/ic902189g
Abstract
The PdII dimers [(2-phenylpyridine)Pd(μ-X)]2 and [(2-p-tolylpyridine)Pd(μ-X)]2 (X = OAc or TFA) do not exhibit the expected planar geometry (of approximate D2h symmetry) but instead resemble an open “clamshell” in which the acetate ligands are perpendicular to the plane containing the Pd atoms and 2-arylpyridine ligands, with the Pd atoms brought quite close to one another (approximate distance 2.85 Å). The molecules adopt this unusual geometry in part because of a d8−d8 bonding interaction between the two Pd centers. The Pd−Pd dimers exhibit two successive one-electron oxidations: PdII−PdII to PdII−PdIII to PdIII−PdIII. Photophysical measurements reveal clear differences in the UV−visible and low-temperature fluorescence spectra between the clamshell dimers and related planar dimeric [(2-phenylpyridine)Pd(μ-Cl)]2 and monomeric [(2-phenylpyridine)Pd(en)][Cl] (en = ethylenediamine) complexes that do not have any close Pd−Pd contacts. Density functional theory and atoms in molecules analyses confirm the presence of a Pd−Pd bonding interaction in [(2-phenylpyridine)Pd(μ-X)]2 and show that the highest occupied molecular orbital is a dz2 σ* Pd−Pd antibonding orbital, while the lowest unoccupied molecular orbital and close-lying empty orbitals are mainly located on the 2-phenylpyridine rings. Computational analyses of other PdII−PdII dimers that have short Pd−Pd distances yield an orbital ordering similar to that of [(2-phenylpyridine)Pd(μ-X)]2, but quite different from that found for d8−d8 dimers of Rh, Ir, and Pt. This difference in orbital ordering arises because of the unusually large energy gap between the 4d and 5p orbitals in Pd and may explain why Pd d8−d8 dimers do not exhibit the distinctive photophysical properties of related Rh, Ir, and Pt species.Keywords
This publication has 51 references indexed in Scilit:
- Highlights from Recent Work on Metal−Metal BondsInorganic Chemistry, 1998
- Chain Conformation and Metal…Metal Contacts in Dimers and Stacks of d8‐ML4Complexes: Electronic EffectsChemistry – A European Journal, 1997
- Linear-Chain Structures of Platinum(II) Diimine ComplexesInorganic Chemistry, 1997
- On the Bonding Nature of the M.cntdot. .cntdot. .cntdot.M Interactions in Dimers of Square-Planar Pt(II) and Rh(I) ComplexesJournal of the American Chemical Society, 1995
- Pyrophosphito-bridged diplatinum chemistryAccounts of Chemical Research, 1989
- Photophysical properties of the lowest electronic excited states of binuclear rhodium(I) isocyanide complexesCoordination Chemistry Reviews, 1982
- Spectroscopic properties and redox chemistry of the phosphorescent excited state of octahydrotetrakis(phosphorus pentoxide)diplatinate(4-) ion (Pt2(P2O5)4H84-)Journal of the American Chemical Society, 1981
- Further Studies of the Spectroscopic Properties and Photochemistry of Binuclear Rhodium(I) Isocyanide ComplexesPublished by American Chemical Society (ACS) ,1979
- Characterization of oligomers of tetrakis(phenyl isocyanide)rhodium(I) in acetonitrile solutionJournal of the American Chemical Society, 1975
- Crystal structure of the red form of 2,2′-bipyridyldichloroplatinum(II)J. Chem. Soc., Dalton Trans., 1974