Inorganic Chemistry, volume 55, issue 23, pages 12391-12399
Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions
Bongki Shin
1
,
K. D. Sutherlin
2
,
Takehiro Ohta
3
,
T. Ogura
3
,
Edward I. Solomon
2, 4
,
Jae-Heung Cho
1
3
Picobiology Institute, Graduate School of Life Science, University of Hyogo, RSC-UH LP Center, Hyogo 679-5148, Japan
|
Publication type: Journal Article
Publication date: 2016-11-15
Journal:
Inorganic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 4.6
ISSN: 00201669, 1520510X
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
The reactivity of mononuclear metal-hydroperoxo adducts has fascinated researchers in many areas due to their diverse biological and catalytic processes. In this study, a mononuclear cobalt(III)-peroxo complex bearing a tetradentate macrocyclic ligand, [CoIII(Me3-TPADP)(O2)]+ (Me3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane), was prepared by reacting [CoII(Me3-TPADP)(CH3CN)2]2+ with H2O2 in the presence of triethylamine. Upon protonation, the cobalt(III)-peroxo intermediate was converted into a cobalt(III)-hydroperoxo complex, [CoIII(Me3-TPADP)(O2H)(CH3CN)]2+. The mononuclear cobalt(III)-peroxo and -hydroperoxo intermediates were characterized by a variety of physicochemical methods. Results of electrospray ionization mass spectrometry clearly show the transformation of the intermediates: the peak at m/z 339.2 assignable to the cobalt(III)-peroxo species disappears with concomitant growth of the peak at m/z 190.7 corresponding to the cobalt(III)-hydroperoxo complex (with bound CH3CN). Isotope labeling experiments further support the existence of the cobalt(III)-peroxo and -hydroperoxo complexes. In particular, the O-O bond stretching frequency of the cobalt(III)-hydroperoxo complex was determined to be 851 cm-1 for 16O2H samples (803 cm-1 for 18O2H samples), and its Co-O vibrational energy was observed at 571 cm-1 for 16O2H samples (551 cm-1 for 18O2H samples; 568 cm-1 for 16O22H samples) by resonance Raman spectroscopy. Reactivity studies performed with the cobalt(III)-peroxo and -hydroperoxo complexes in organic functionalizations reveal that the latter is capable of conducting oxygen atom transfer with an electrophilic character, whereas the former exhibits no oxygen atom transfer reactivity under the same reaction conditions. Alternatively, the cobalt(III)-hydroperoxo complex does not perform hydrogen atom transfer reactions, while analogous low-spin Fe(III)-hydroperoxo complexes are capable of this reactivity. Density functional theory calculations indicate that this lack of reactivity is due to the high free energy cost of O-O bond homolysis that would be required to produce the hypothetical Co(IV)-oxo product.
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Citations by publishers
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1 publication, 2.44%
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- We do not take into account publications without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
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Shin B. et al. Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions // Inorganic Chemistry. 2016. Vol. 55. No. 23. pp. 12391-12399.
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Shin B., Sutherlin K. D., Ohta T., Ogura T., Solomon E. I., Cho J. Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions // Inorganic Chemistry. 2016. Vol. 55. No. 23. pp. 12391-12399.
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TY - JOUR
DO - 10.1021/acs.inorgchem.6b02288
UR - https://doi.org/10.1021/acs.inorgchem.6b02288
TI - Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions
T2 - Inorganic Chemistry
AU - Shin, Bongki
AU - Sutherlin, K. D.
AU - Ohta, Takehiro
AU - Ogura, T.
AU - Solomon, Edward I.
AU - Cho, Jae-Heung
PY - 2016
DA - 2016/11/15
PB - American Chemical Society (ACS)
SP - 12391-12399
IS - 23
VL - 55
SN - 0020-1669
SN - 1520-510X
ER -
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@article{2016_Shin,
author = {Bongki Shin and K. D. Sutherlin and Takehiro Ohta and T. Ogura and Edward I. Solomon and Jae-Heung Cho},
title = {Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions},
journal = {Inorganic Chemistry},
year = {2016},
volume = {55},
publisher = {American Chemical Society (ACS)},
month = {nov},
url = {https://doi.org/10.1021/acs.inorgchem.6b02288},
number = {23},
pages = {12391--12399},
doi = {10.1021/acs.inorgchem.6b02288}
}
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MLA
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Shin, Bongki, et al. “Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions.” Inorganic Chemistry, vol. 55, no. 23, Nov. 2016, pp. 12391-12399. https://doi.org/10.1021/acs.inorgchem.6b02288.