The thermochemistry of london dispersion-driven transition metal reactions: getting the 'right answer for the right reason'.

ABSTRACT: Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies were measured by isotherm titration calorimetry (ITC) and theoretically 'back-corrected' to yield 0 K gas-phase reaction energies (ΔE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source of

SUBMITTER: Hansen A 

PROVIDER: S-EPMC4234214 | biostudies-literature | 2014 Oct

REPOSITORIES: biostudies-literature