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Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions

Journal Article · · Inorganic Chemistry
 [1];  [2];  [3];  [3];  [4];  [1]
  1. Daegu Gyeongbuk Inst. of Science and Technology, Daegu (Korea, Republic of). Dept. of Emerging Materials Science
  2. Stanford Univ., CA (United States). Dept. of Chemistry
  3. Univ. of Hyogo (Japan). Picobiology Inst., Graduate School of Life Science
  4. Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
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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 16O2 2H 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 function 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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE; National Institutes of Health (NIH)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1361127
Alternate ID(s):
OSTI ID: 1361125
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 23 Vol. 55; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (8)

Catalytic Applications of Pyridine-Containing Macrocyclic Complexes: Catalytic Applications of Pyridine-Containing Macrocyclic Complexes journal July 2017
A mononuclear manganese( iii )–hydroperoxo complex: synthesis by activating dioxygen and reactivity in electrophilic and nucleophilic reactions journal January 2018
A unified understanding of the direct coordination of NO to first-transition-row metal centers in metal–ligand complexes journal January 2017
Bio-mimetic oxygen separation via a hollow fiber membrane contactor with O 2 carrier solutions journal January 2018
One step phenol synthesis from benzene catalysed by nickel( ii ) complexes journal January 2019
Single-step benzene hydroxylation by cobalt( ii ) catalysts via a cobalt( iii )-hydroperoxo intermediate journal January 2020
Oxidative C–N bond cleavage of (2-pyridylmethyl)amine-based tetradentate supporting ligands in ternary cobalt( ii )–carboxylate complexes journal January 2020
Nucleophilic reactivity of a mononuclear cobalt( iii )–bis( tert -butylperoxo) complex journal January 2020

Figures / Tables (9)

Scheme 1(p. 1)figure Scheme 1
Figure 5(p. 2)figure Figure 5
Figure 1(p. 3)figure Figure 1
Scheme 2(p. 3)figure Scheme 2
Figure 2(p. 4)figure Figure 2
Figure 3(p. 4)figure Figure 3
Figure 4(p. 5)figure Figure 4
Scheme 3(p. 6)figure Scheme 3
Table 1(p. 7)table Table 1

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