title: Hangman salophens.
abstract: We report here a modular approach for the construction of a new class of compounds, the Hangman salophens. In the Hangman motif, an acid-base functionality "hangs" over the face of a redox cofactor. In contrast to more synthetically intractable porphyrin-based Hangman systems, Hangman salophens permit the facile control of their proton and redox properties for the study of the proton-coupled electron transfer (PCET) activation of small molecules. By investigating the catalase-like disproportionation of H2O2, we show that the presence (1) of a strong proton-donating hanging group (i.e., carboxylic acid) and (2) of electron-donating groups on the redox-active salen imparts significant catalytic activity for the O-O bond activation of small molecule substrates. The contribution of the new ligand framework to furthering our understanding of how PCET can be implemented in the design of active/selective catalysts will be discussed.
authors.affiliation: Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
authors.forename: Shih-Yuan
authors.initials: SY
authors.lastname: Liu
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Nocera
mesh_terms: D002374:Catalase / Q000737:chemistry / Q000378:metabolism; D002384:Catalysis; D004563:Electrochemistry; D008024:Ligands; D010084:Oxidation-Reduction; D012459:Salicylates / Q000737:chemistry*; D014966:Xanthenes / Q000737:chemistry
chemical_list: D008024:Ligands; D012459:Salicylates; D014966:Xanthenes; C090416:salophen; D002374:Catalase