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Isolation of a Square Pyramidal Bis(amidophenolate)-Supported As(III)-Cation: Coordination-Induced Electromerism at
Simon B H Karnbrock1, Jan F Köster1, Christopher Golz1
1Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.
Abstract:
The synthesis and structural characterization of a slightly distorted square pyramidal arsenium cation is reported. Spectroscopic, crystallographic, and computational evidence indicate that coordination of typical Lewis bases to the As(III)-center induces its oxidation to As(V) with concomitant reduction of the supporting, redox-active bis(amidophenolate) ligand. That reaction is reversible and represents a well-defined example of base-induced electromerism in an As-complex. Single electron reduction of the same As(III) species initially generates a ligand-centered radical, which is persistent enough to be observed by EPR but slowly decays to a heterodimer. Preliminary experiments demonstrate the utility of the As(III)-cation as initiator for transfer hydrogenation reactions.
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