Oxygen activation at a dicobalt centre of a dipyridylethane naphthyridine complex

Casey N. Brodsky; Guillaume Passard; Andrew M. Ullman; David E. Jaramillo; Eric D. Bloch; Michael Huynh; David Gygi; Cyrille Costentin; Daniel G. Nocera

doi:10.1039/c8dt01598h

Oxygen activation at a dicobalt centre of a dipyridylethane naphthyridine complex

Casey N. Brodsky, Guillaume Passard, Andrew M. Ullman, David E. Jaramillo, Eric D. Bloch, Michael Huynh, David Gygi, Cyrille Costentin, Daniel G. Nocera

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9 Scopus citations

Abstract

The mechanism of oxygen activation at a dicobalt bis-μ-hydroxo core is probed by the implementation of synthetic methods to isolate reaction intermediates. Reduction of a dicobalt(iii,iii) core ligated by the polypyridyl ligand dipyridylethane naphthyridine (DPEN) by two electrons and subsequent protonation result in the release of one water moiety to furnish a dicobalt(ii,ii) center with an open binding site. This reduced core may be independently isolated by chemical reduction. Variable-temperature ¹H NMR and SQUID magnetometry reveal the reduced dicobalt(ii,ii) intermediate to consist of two low spin Co(ii) centers coupled antiferromagnetically. Binding of O₂ to the open coordination site of the dicobalt(ii,ii) core results in the production of an oxygen adduct, which is proposed to be a dicobalt(iii,iii) peroxo. Electrochemical studies show that the addition of two electrons results in cleavage of the O-O bond.

Original language	English
Pages (from-to)	11903-11908
Number of pages	6
Journal	Dalton Transactions
Volume	47
Issue number	34
DOIs	https://doi.org/10.1039/c8dt01598h
State	Published - 2018
Externally published	Yes

Funding

This material is based upon work supported by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0017619. C. N. B. acknowledges the National Science Foundation’s Graduate Research Fellowship Program. We are grateful to Chris Lemon for guidance with VT NMR, Robert Halbach for assistance in crystal structure refinement, Ryan Cowley for help with resonance Raman, and Professor Kit Cummins for helpful discussions. This material is based upon work supported by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0017619. C. N. B. acknowledges the National Science Foundation's Graduate Research Fellowship Program. We are grateful to Chris Lemon for guidance with VT NMR, Robert Halbach for assistance in crystal structure refinement, Ryan Cowley for help with resonance Raman, and Professor Kit Cummins for helpful discussions.

Funders	Funder number
Office of Basic Energy Sciences	DE-SC0017619
U.S. Department of Energy Office of Science
National Science Foundation
U.S. Department of Energy
Office of Science

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title = "Oxygen activation at a dicobalt centre of a dipyridylethane naphthyridine complex",

abstract = "The mechanism of oxygen activation at a dicobalt bis-μ-hydroxo core is probed by the implementation of synthetic methods to isolate reaction intermediates. Reduction of a dicobalt(iii,iii) core ligated by the polypyridyl ligand dipyridylethane naphthyridine (DPEN) by two electrons and subsequent protonation result in the release of one water moiety to furnish a dicobalt(ii,ii) center with an open binding site. This reduced core may be independently isolated by chemical reduction. Variable-temperature 1H NMR and SQUID magnetometry reveal the reduced dicobalt(ii,ii) intermediate to consist of two low spin Co(ii) centers coupled antiferromagnetically. Binding of O2 to the open coordination site of the dicobalt(ii,ii) core results in the production of an oxygen adduct, which is proposed to be a dicobalt(iii,iii) peroxo. Electrochemical studies show that the addition of two electrons results in cleavage of the O-O bond.",

author = "Brodsky, {Casey N.} and Guillaume Passard and Ullman, {Andrew M.} and Jaramillo, {David E.} and Bloch, {Eric D.} and Michael Huynh and David Gygi and Cyrille Costentin and Nocera, {Daniel G.}",

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year = "2018",

doi = "10.1039/c8dt01598h",

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T1 - Oxygen activation at a dicobalt centre of a dipyridylethane naphthyridine complex

AU - Brodsky, Casey N.

AU - Passard, Guillaume

AU - Ullman, Andrew M.

AU - Jaramillo, David E.

AU - Bloch, Eric D.

AU - Huynh, Michael

AU - Gygi, David

AU - Costentin, Cyrille

AU - Nocera, Daniel G.

PY - 2018

Y1 - 2018

N2 - The mechanism of oxygen activation at a dicobalt bis-μ-hydroxo core is probed by the implementation of synthetic methods to isolate reaction intermediates. Reduction of a dicobalt(iii,iii) core ligated by the polypyridyl ligand dipyridylethane naphthyridine (DPEN) by two electrons and subsequent protonation result in the release of one water moiety to furnish a dicobalt(ii,ii) center with an open binding site. This reduced core may be independently isolated by chemical reduction. Variable-temperature 1H NMR and SQUID magnetometry reveal the reduced dicobalt(ii,ii) intermediate to consist of two low spin Co(ii) centers coupled antiferromagnetically. Binding of O2 to the open coordination site of the dicobalt(ii,ii) core results in the production of an oxygen adduct, which is proposed to be a dicobalt(iii,iii) peroxo. Electrochemical studies show that the addition of two electrons results in cleavage of the O-O bond.

AB - The mechanism of oxygen activation at a dicobalt bis-μ-hydroxo core is probed by the implementation of synthetic methods to isolate reaction intermediates. Reduction of a dicobalt(iii,iii) core ligated by the polypyridyl ligand dipyridylethane naphthyridine (DPEN) by two electrons and subsequent protonation result in the release of one water moiety to furnish a dicobalt(ii,ii) center with an open binding site. This reduced core may be independently isolated by chemical reduction. Variable-temperature 1H NMR and SQUID magnetometry reveal the reduced dicobalt(ii,ii) intermediate to consist of two low spin Co(ii) centers coupled antiferromagnetically. Binding of O2 to the open coordination site of the dicobalt(ii,ii) core results in the production of an oxygen adduct, which is proposed to be a dicobalt(iii,iii) peroxo. Electrochemical studies show that the addition of two electrons results in cleavage of the O-O bond.

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JO - Dalton Transactions

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ER -

Oxygen activation at a dicobalt centre of a dipyridylethane naphthyridine complex

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