Delocalization and Valence Tautomerism in Vanadium Tris(iminosemiquinone) Complexes |
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| Authors: | Prof Jesper Bendix Dr Kensha Marie Clark |
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| Affiliation: | 1. Department of Chemistry, University of Copenhagen, Copenhagen, Denmark;2. Department of Chemistry, University of California, Irvine, Irvine, CA, USA;3. Chevron Phillips Chemical Company, LP, Building 94-E, PRC, Bartlesville, OK, USA |
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| Abstract: | To survey the noninnocence of bis(arylimino) acenaphthene (BIAN) ligands (L) in complexes with early metals, the homoleptic vanadium complex, V(L)3] ( 1 ), and its monocation, V(L)3]PF6 ( 2 ), were synthesized. These complexes were found to have a very rich electronic behavior, whereby 1 displays strong electronic delocalization and 2 can be observed in unprecedented valence tautomeric forms. The oxidation states of the metal and ligand components in these complexes were assigned by using spectroscopic, crystallographic, and magnetic analyses. Complex 1 was identified as VIV(Lred)(L.)2] (Lred=N,N′‐bis(3,5‐dimethylphenylamido)acenaphthylene; L.=N,N′‐bis(3,5‐dimethylphenylimino)acenaphthenesemiquinonate). Complex 2 was determined to be VV(Lred)(L.)2]+ at T<150 K and VIV(L.)3]+ at T>150 K. Cyclic voltammetry experiments reveal six quasi‐reversible processes, thus indicating the potential of this metal–ligand combination in catalysis or materials applications. |
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| Keywords: | mixed-valent compounds noninnocent ligands redox-active ligands valence tautomerism vanadium |
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