SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

Developing
more efficient catalysts remains one of the primary
targets of organometallic chemists. To accelerate reaching this goal,
effective molecular descriptors and visualization tools can represent
a remarkable aid. Here, we present a Web application for analyzing
the catalytic pocket of metal complexes using topographic steric maps
as a general and unbiased descriptor that is suitable for every class
of catalysts. To show the broad applicability of our approach, we
first compared the steric map of a series of transition metal complexes
presenting popular mono-, di-, and tetracoordinated ligands and three
classic zirconocenes. This comparative analysis highlighted similarities
and differences between totally unrelated ligands. Then, we focused
on a recently developed Fe­(II) catalyst that is active in the asymmetric
transfer hydrogenation of ketones and imines. Finally, we expand the
scope of these tools to rationalize the inversion of enantioselectivity
in enzymatic catalysis, achieved by point mutation of three amino
acids of mononuclear p-hydroxymandelate synthase.