From Catalyst Design to Molecular Devices: Theory and Experiments
DOI:
https://doi.org/10.2533/chimia.1999.19Abstract
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+.
A tripodal 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.
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Copyright (c) 1999 Swiss Chemical Society
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