From catalyst design to molecular devices: Theory and experiments

Abstract

Three different topics are presented herein. With the help of molecular-orbital analysis, the unique geometry and catalytic properties of d0 bent-metallocenes was analyzed in search for cyclopentadienyl substitutes. To overcome the inherent racemization of coordinatively unsaturated piano-stool complexes, a ten-electron donor ligand was designed. This ligand incorporates an arene bearing two tethers: a phosphine and an imine (abbreviated PArN). It was shown that upon η6:η1:η1-coordination of PArN to ruthenium, a configurationally stable piano-stool complex results [Ru(η6:η1:η1-PArN)L]n+. Atripodal dodecadentate ligand, incorporating three soft bipyridine donors as well as three harder salicylamide chelates, was synthesized. This ligand allowed the investigation of the iron release from ferric enterobactin, suggesting a protonation/translocation into a salicylate-binding mode. In the presence of a single iron ion and depending on its oxidation mode, it was shown that this system displays switch-like properties.