The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

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 (Δ E ). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source of error in theoretical thermochemistry protocols. The (‘back‐corrected’) experimental reaction energies were used to benchmark (dispersion‐corrected) density functional and wave function theory methods. Particularly, we investigated whether the atom‐pairwise D3 dispersion correction is also accurate for transition metal chemistry, and how accurately recently developed local coupled‐cluster methods describe the important long‐range electron correlation contributions. Both, modern dispersion‐corrected density functions (e.g., PW6B95‐D3(BJ) or B3LYP‐NL), as well as the now possible DLPNO‐CCSD(T) calculations, are within the ‘experimental’ gas phase reference value. The remaining uncertainties of 2–3 kcal mol −1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising.