Dioxygen bound cobalt corroles

Kaustuv Mittra; Biswajit Mondal; Atif Mahammed; Zeev Gross; Abhishek Dey

doi:10.1039/c6cc06982g

Dioxygen bound cobalt corroles

Kaustuv Mittra, Biswajit Mondal, Atif Mahammed, Zeev Gross, Abhishek Dey

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25 Scopus citations

Abstract

Two cobalt-dioxygen adducts, [CoH₈]-O₂ and [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]-O₂ is somewhat stronger than in [CoCl₈]-O₂ and its O-O is weaker, but also that the differences are truly minute (8-10 cm⁻¹ for 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.

Original language	English
Pages (from-to)	877-880
Number of pages	4
Journal	Chemical Communications
Volume	53
Issue number	5
DOIs	https://doi.org/10.1039/c6cc06982g
State	Published - 1 Jan 2017
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Electronic, Optical and Magnetic Materials
Ceramics and Composites
General Chemistry
Surfaces, Coatings and Films
Metals and Alloys
Materials Chemistry

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title = "Dioxygen bound cobalt corroles",

abstract = "Two cobalt-dioxygen adducts, [CoH8]-O2 and [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]-O2 is somewhat stronger than in [CoCl8]-O2 and its O-O is weaker, but also that the differences are truly minute (8-10 cm−1 for 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.",

author = "Kaustuv Mittra and Biswajit Mondal and Atif Mahammed and Zeev Gross and Abhishek Dey",

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year = "2017",

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doi = "10.1039/c6cc06982g",

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T1 - Dioxygen bound cobalt corroles

AU - Mittra, Kaustuv

AU - Mondal, Biswajit

AU - Mahammed, Atif

AU - Gross, Zeev

AU - Dey, Abhishek

N1 - Publisher Copyright: © The Royal Society of Chemistry.

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Two cobalt-dioxygen adducts, [CoH8]-O2 and [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]-O2 is somewhat stronger than in [CoCl8]-O2 and its O-O is weaker, but also that the differences are truly minute (8-10 cm−1 for 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.

AB - Two cobalt-dioxygen adducts, [CoH8]-O2 and [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]-O2 is somewhat stronger than in [CoCl8]-O2 and its O-O is weaker, but also that the differences are truly minute (8-10 cm−1 for 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.

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SN - 1359-7345

VL - 53

SP - 877

EP - 880

JO - Chemical Communications

JF - Chemical Communications

IS - 5

ER -

Dioxygen bound cobalt corroles

Abstract

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