Semiautomated Transition State Localization for Organometallic Complexes with Semiempirical Quantum Chemical Methods

We present an efficient computational protocol for robust transition state localization that can be routinely applied to complex (organometallic) reactions. The capabilities of the combination of extended tight-binding semiempirical methods (GFNn-xTB) with a state-of-the-art transition state localization algorithm (mGSM) is demonstrated on a modified version of the MOBH35 benchmark set, consisting of 29 organometallic reactions and transition states. Furthermore, for three examples we demonstrate how error-prone the conventional (manual) approach based on chemical intuition can be and how errors are avoided by a semiautomated generation of reaction profiles. The performance of the GFNn-xTB methods is carefully assessed and compared with that of the widely used PM6-D3H4 and PM7 semiempirical methods. The GFNn-xTB methods show much higher success rates of 89.7% (GFN1-xTB) and 86.2% (GFN2-xTB) compared with 72.4% for PM6-D3H4 and 69.0% for PM7. The barrier heights and reaction energies are computed with much better accuracy at reduced computational cost for the GFNn-xTB methods compared with the PMx methods, allowing a semiquantitative assessment of possible reaction pathways already at a semiempirical level. The mean error of GFN2-xTB for the barrier heights (8.2 kcal mol(-1)) is close to what low-cost density functional approximations provide and substantially smaller than the corresponding error of the competitor methods.