LAUSR

Abstract Metal carbene complexes represent an ubiquitous class of compounds in organomettalic chemistry able to trigger a wealth of catalytic reactions of both fundamental and industrial processes. By resorting to first principles approaches, we focus on the fundamental features of these complexes in which the metal center can be either Hf, Ti or Zr. These specific systems show interesting features in their neutral and charged (+1) states. Yet, we provide evidence of the fact that the nature of the metallic ion does not have a significant impact on the structure of the ligand. Conversely, the removal of one electron (charge state +1) induces a perturbation of the ligand conformation and this, in turn, is prone to affect the catalytic properties of the complex, carrying the singly occupied electronic level (spin distribution of the system) delocalized over the carbene ligand.