Computational organometallic chemistry of ruthenium complexes for materials and medicinal applications

Ruthenium organometallic complexes offer versatile platforms for applications in materials science and medicinal chemistry. This contribution presents two computational studies on Ru systems in distinct applied contexts. The first examines η⁴-diene ruthenium tricarbonyl compounds as molecular precursors for photo-assisted chemical vapor deposition of Ru-based materials. DFT, TD-DFT, excited-state potential-energy profiles, natural transition orbital analysis, and EDA–NOCV calculations were used to map competing CO- and diene-loss pathways after photoexcitation, showing how ligand identity and coordination flexibility control precursor activation. The second study addresses Ru(II)-catalyzed C–H alkenylation of trypanocidal naphthoquinones with ethenesulfonyl fluoride, installing sulfur(VI) fluoride exchange (SuFEx)-ready groups for modular diversification of bioactive quinone scaffolds. Benchmarking density functionals against DLPNO-CCSD(T) reference energies clarifies the catalytic cycle and identifies C–H activation, Ru speciation, and ligand exchange as key factors controlling turnover.