Comparing Density Functional Theory Metal–Ligand Bond Dissociation Enthalpies with Experimental Solution-Phase Enthalpies of Activation for Bond Dissociation

The predictive ability of density functional theory is
fundamental
to its usefulness in chemical applications. Recent work has compared
solution-phase enthalpies of activation for metal–ligand bond
dissociation to enthalpies of reaction for bond dissociation, and
the present work continues those comparisons for 43 density functional
methods. The results for ligand dissociation enthalpies of 30 metal–ligand
complexes tested in this work reveal significant inadequacies of some
functionals as well as challenges from the dispersion corrections
to some functionals. The analysis presented here demonstrates the
excellent performance of a recent density functional, M11plus, which
contains nonlocal rung-3.5 correlation. We also find a good agreement
between theory and experiment for some functionals without empirical
dispersion corrections such as M06, r2SCAN, M06-L, and
revM11, as well as good performance for some functionals with added
dispersion corrections such as ωB97X-D (which always has a correction)
and BLYP, B3LYP, CAM-B3LYP, and PBE0 when the optional dispersion
corrections are added.