Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity

Amanda R. Corcos; Omar Villanueva; Richard C. Walroth; Savita K. Sharma; John Bacsa; Kyle M. Lancaster; Cora E. MacBeth; John F. Berry

doi:10.1021/jacs.5b12643

Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity

Amanda R. Corcos
, Omar Villanueva
, Richard C. Walroth
, Savita K. Sharma
, John Bacsa
, Kyle M. Lancaster
, Cora E. MacBeth
, John F. Berry

School of Science (Behrend)

Research output: Contribution to journal › Article › peer-review

86 Scopus citations

Abstract

Bimetallic (Et₄N)₂[Co₂(L)₂], (Et₄N)₂[1] (where (L)^3- = (N(o-PhNC(O)ⁱPr)₂)^3-) reacts with 2 equiv of O₂ to form the monometallic species (Et₄N)[Co(L)O₂], (Et₄N)[3]. A crystallographically characterized analog (Et₄N)₂[Co(L)CN], (Et₄N)₂[2], gives insight into the structure of [3]^1-. Magnetic measurements indicate [2]^2- to be an unusual high-spin Co^II-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3]^1- to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3]^1- features a high-spin Co^II center; the net S = 1/2 spin state arises after the Co electrons couple to both the O₂^•- and the aminyl radical on redox non-innocent (L^•)^2-. Dianion [1]^2- shows both nucleophilic and electrophilic catalytic reactivity upon activation of O₂ due to the presence of both a high-energy, filled O₂^- π∗ orbital and an empty low-lying O₂^- π∗ orbital in [3]^1-.

Original language	English (US)
Pages (from-to)	1796-1799
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	6
DOIs	https://doi.org/10.1021/jacs.5b12643
State	Published - Feb 17 2016

All Science Journal Classification (ASJC) codes

Catalysis
Biochemistry
General Chemistry
Colloid and Surface Chemistry

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10.1021/jacs.5b12643

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Corcos, A. R., Villanueva, O., Walroth, R. C., Sharma, S. K., Bacsa, J., Lancaster, K. M., MacBeth, C. E., & Berry, J. F. (2016). Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity. Journal of the American Chemical Society, 138(6), 1796-1799. https://doi.org/10.1021/jacs.5b12643

@article{cb0f4c86cbe9496c9c6a00cb4df588b5,

title = "Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity",

abstract = "Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)3- = (N(o-PhNC(O)iPr)2)3-) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3]1-. Magnetic measurements indicate [2]2- to be an unusual high-spin CoII-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3]1- to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3]1- features a high-spin CoII center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2•- and the aminyl radical on redox non-innocent (L•)2-. Dianion [1]2- shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2- π∗ orbital and an empty low-lying O2- π∗ orbital in [3]1-.",

author = "Corcos, \{Amanda R.\} and Omar Villanueva and Walroth, \{Richard C.\} and Sharma, \{Savita K.\} and John Bacsa and Lancaster, \{Kyle M.\} and MacBeth, \{Cora E.\} and Berry, \{John F.\}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = feb,

day = "17",

doi = "10.1021/jacs.5b12643",

language = "English (US)",

volume = "138",

pages = "1796--1799",

journal = "Journal of the American Chemical Society",

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Corcos, AR, Villanueva, O, Walroth, RC, Sharma, SK, Bacsa, J, Lancaster, KM, MacBeth, CE & Berry, JF 2016, 'Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity', Journal of the American Chemical Society, vol. 138, no. 6, pp. 1796-1799. https://doi.org/10.1021/jacs.5b12643

Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity. / Corcos, Amanda R.; Villanueva, Omar; Walroth, Richard C. et al.
In: Journal of the American Chemical Society, Vol. 138, No. 6, 17.02.2016, p. 1796-1799.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand

T2 - Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity

AU - Corcos, Amanda R.

AU - Villanueva, Omar

AU - Walroth, Richard C.

AU - Sharma, Savita K.

AU - Bacsa, John

AU - Lancaster, Kyle M.

AU - MacBeth, Cora E.

AU - Berry, John F.

PY - 2016/2/17

Y1 - 2016/2/17

N2 - Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)3- = (N(o-PhNC(O)iPr)2)3-) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3]1-. Magnetic measurements indicate [2]2- to be an unusual high-spin CoII-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3]1- to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3]1- features a high-spin CoII center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2•- and the aminyl radical on redox non-innocent (L•)2-. Dianion [1]2- shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2- π∗ orbital and an empty low-lying O2- π∗ orbital in [3]1-.

AB - Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)3- = (N(o-PhNC(O)iPr)2)3-) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3]1-. Magnetic measurements indicate [2]2- to be an unusual high-spin CoII-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3]1- to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3]1- features a high-spin CoII center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2•- and the aminyl radical on redox non-innocent (L•)2-. Dianion [1]2- shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2- π∗ orbital and an empty low-lying O2- π∗ orbital in [3]1-.

UR - https://www.scopus.com/pages/publications/84959036391

UR - https://www.scopus.com/pages/publications/84959036391#tab=citedBy

U2 - 10.1021/jacs.5b12643

DO - 10.1021/jacs.5b12643

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AN - SCOPUS:84959036391

SN - 0002-7863

VL - 138

SP - 1796

EP - 1799

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 6

ER -

Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity

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