A new simplifying approach to molecular geometry description: the vectorial bond-valence model

A method to describe, analyze and even predict the coordination geometries of metal complexes is proposed, based on previous well established concepts such as bond valence and valence‐shell electron‐pair repulsion (VSEPR). The idea behind the method is the generalization of the scalar bond‐valence concept into a vector quantity, the bond‐valence vector (BVV), with the innovation that the multidentate ligands are represented by their resultant BVVs. Complex n‐ligand coordination spheres (frequently indescribable at the atomic level) reduce to much simpler ones when analyzed in BVV space, with the bonus of a better applicability of the VSEPR predictions. The geometrical implications of the BVV description are analyzed for the cases of n = 2 and 3 (n = number of ligands), and the validity of its predictions, checked for a large number of metal complexes.