2024/11/11 by S. M. Supundrika Subasinghe, Maxim R. Radzhabov, Neal P. Mankad · 1 voice · 1 citation
Materials Science · Chemistry · #Machine Learning in Materials Science #Thermal and Kinetic Analysis #Inorganic and Organometallic Chemistry
paper · doi:10.1021/acs.organomet.4c00285
Our lab has studied a complex with an Al–Fe bond capable of cooperative substrate activation processes. This reactivity was previously found to depend on Al–Fe homolytic bond dissociation followed by substrate coordination to the Al III center of the resulting redox noninnocent radical intermediate. The current study investigates ligand influences on the Al–Fe bond dissociation free energy (BDFE Al–Fe ) and the Gibbs free energy of H 2 O coordination at aluminum (Δ G OH 2 ) for a series of variants with systematic changes in their ligand substitution patterns. DFT calculations combined with multivariate linear regression analysis provided predictive models for ligand effects on both BDFE Al–Fe and Δ G Al–OH 2 for three synthetically tunable positions in the molecular architecture when using appropriate electronic (σ para, σ meta ) and steric (wSterimol, % V bur ) descriptors. Chemical interpretations of the predictive models were facilitated by the use of these intuitive descriptors. Linear scaling relationships relating BDFE Al–Fe and Δ G OH 2 provided further insight. We expect our findings to inform designs of future Al-containing heterobinuclear complexes for small molecule activation processes and cleavage reactions of strong or inert bonds.