title: Dioxygen bound cobalt corroles.
abstract: Two cobalt-dioxygen adducts, [CoH8]-O2and [CoCl8]-O2, chelated by electron-rich and electron-poor corroles, respectively, were isolated in solution. Characterization by resonance Raman (rR) and EPR spectroscopy, together with DFT analyses, point towards (corrole) cobalt(iii)-O2˙-structures in both cases. The most significant insight was obtained from the Co-O and O-O stretching frequencies, which revealed that the Co-O bond in [CoH8]-O2is somewhat stronger than in [CoCl8]-O2and its O-O is weaker, but also that the differences are truly minute (8-10 cm-1for the O-O stretch). These conclusions are vital regarding the various applications that rely on efficient reduction of molecular oxygen. In particular, these kinds of cobalt complexes are perfectly suited for serving as electrocatalysts that may be tuned to operate at minimal overpotential without losing almost anything in terms of activity.
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, India 700032. icad@iacs.res.in.
authors.forename: Kaustuv
authors.initials: K
authors.lastname: Mittra
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, India 700032. icad@iacs.res.in.
authors.forename: Biswajit
authors.initials: B
authors.lastname: Mondal
authors.affiliation: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel. chr10zg@techunix.technion.ac.il.
authors.forename: Atif
authors.initials: A
authors.lastname: Mahammed
authors.affiliation: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel. chr10zg@techunix.technion.ac.il.
authors.forename: Zeev
authors.initials: Z
authors.lastname: Gross
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, India 700032. icad@iacs.res.in.
authors.forename: Abhishek
authors.initials: A
authors.lastname: Dey