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Updated: Apr 21, 2026
Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Redox activity and π bonding in a tripodal seven-coordinate molybdenum(VI) tris(amidophenolate)
Travis Marshall-Roth1, Seth N Brown
1Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall. and University of Notre Dame, Notre Dame, IN 46556-5670, USA. Seth.N.Brown.114@nd.edu.
Abstract:
A tris(aminophenol), tris(2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)amino-4-methylphenyl)amine, MeClampH6, is prepared in three steps from tri-p-tolylamine. The ligand reacts with dioxomolybdenum(VI) bis(acetylacetonate) to form an oxo-free heptadentate complex, (MeClamp)Mo, with a capped octahedral geometry. The molybdenum is formally in the +6 oxidation state, with significant π donation of the amidophenolates, as judged by intraligand bond distances. Two ligand-based oxidations and one metal-centered reduction are observed by cyclic voltammetry. Analysis of the optical spectrum of the compound gives an estimate of the energetic stabilization of the ligand π orbitals by bonding to the molybdenum of approximately 0.9 eV, corresponding to about 40 kcal mol(-1) per π bond.
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