Julen Munárriz

A fundamental understanding of chemical bonding through quantum chemistry is a cornerstone of the rational design and development of modern catalytic systems. Advanced quantum-mechanical techniques and bonding descriptors provide a rigorous framework for elucidating the electronic rearrangements, orbital interactions, and potential-energy surfaces that govern transition states and overall reactivity. In particular, the integration of state-of-the-art computational methods, such as density functional theory (DFT) and emerging foundation-level machine-learning potentials (MLPs), offers unprecedented opportunities to map complex reaction spaces and accelerate the discovery of efficient and sustainable catalysts. In homogeneous catalysis, quantum chemical topology (QCT), including the electron localization function and bonding evolution theory, has successfully bridged the gap between traditional electron-pushing formalisms and energy-based descriptors. This is illustrated, for example, by metal–ligand cooperation in challenging processes such as N–H bond activation by ruthenium(II) pincer complexes. Such electronic-structure insight is also instrumental in the design of catalytic systems based on earth-abundant transition metals. We have developed hemilability-controlled manganese and cobalt complexes supported by triazole-based P–N ligands that exhibit high efficiency in dehydrogenative Si–O bond-forming reactions. These transformations proceed through non-classical mechanisms involving frustrated Lewis pairs (FLPs), whose design was guided by the analysis of chemical-bonding indices.