| aRequires a Java-enabled browser to view 3D models.bCalculations were performed at the B3LYP/cc-pVDZ/SCRF(CPCM,solvent=acetone) level (pseudopotential basis sets for the Pd) obtained from the Basis set exchange (D. Feller, J. Comp. Chem., 1996, 17, 1571-1586; K. L. Schuchardt, B. T. Didier, T. Elsethagen, L. Sun, V. Gurumoorthi, J. Chase, J. Li, and T. L. Windus, J. Chem. Inf. Model., 2007, 47, 1045-1052, DOI: 10.1021/ci600510j), with full geometry optimization. The stationary point so located was then corrected for entropic and thermal contributions at the B3LYP/cc-pVDZ/SCRF(CPCM,solvent=acetone) level and is shown as a free energy ΔG‡ barrier in kcal/mol. cAn OAI-PMH compliant institutional data repository, providing access to full information about each system, including the total calculated energies via Gaussian checkpoint and logfile files, coordinates are in CML form, and the metadata conforms to the METS specifications. d AIM analysis. Bond critical points (BCP) shown as small purple spheres, ring critical points (RCP) as yellow spheres and cage critical points (CCP) as green spheres. Artefacts due the Pd pseudopotential close to the Pd centre have been removed for clarity. The bond paths are not as computed, but are shown as connections to the nearest atoms. Particularly significant atoms or BCPs are highlighted with a halo. eA correction for dispersion contributions was made using a single point calculation using the B97D method, which lowers the P2 = (R)-BINAP transition state by a further 0.9 kcal/mol relative to the P2 = (S)-BINAP isomer. fThe B97D energy lowers the P2 = (R)-BINAP transition state by 1.2 kcal/mol relative to the P2 = (S)-BINAP isomer, resulting in the former transition state being predicted to be 0.7 kcal/mol lower in energy than the latter. |