This study examines activation of H2 with PdO. PdO was selected over a bare palladium atom to address whether there exists an intrinsic benefit to involving both the metal and a ligand (i.e., oxygen) in activation. Unrestricted 2nd order M�ller-Plesset (UMP2) perturbation theory with extended pseudopotential (on Pd) and all-electron (H and O) split valence basis sets was deemed an adequate level of theory based on calibration with experimental data. Notably PdH was calculated within 2 wavenumbers of its experimental value, 1952.8cm-1 (expt. 1954.3 cm-1). Modeled reaction pathways include: [2+2] addition across the Pd�O bond, insertion of O into the H�H bond, H atom abstraction/radical rebound, and oxidative addition to Pd. Calculations suggest only the former two are thermodynamically viable and linked by a facile tautomerization pathway. Activation energies imply indirect oxidation through the [2+2] intermediate H�Pd�OH tautomerizing to the slightly more stable insertion adduct, Pd�OH2. UMP2 optimizations and ROMP2 minimum energy crossing points imply triplet reactants readily surface cross to singlet intermediates and products.

H<sub>2</sub> activation by PdO: The oxo ligand utility

247th National Meeting (2014)

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H2 activation by PdO: The oxo ligand utility

H₂ activation by PdO: The oxo ligand utility