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Title: Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

Journal Article · · Nature Chemistry
DOI:https://doi.org/10.1038/nchem.2055· OSTI ID:1291342
 [1];  [1];  [1];  [1];  [2];  [1];  [3];  [4];  [1]
  1. Ewha Womans Univ., Seoul (Korea)
  2. Osaka Univ. and ALCA, Japan Science Technology Agency (JST), Osaka (Japan)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Ewha Womans Univ., Seoul (Korea); Osaka Univ. and ALCA, Japan Science Technology Agency (JST), Osaka (Japan)
+ Show Author Affiliations

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η2:η2-O2)–Mn+ (Mn+ = Sr2+, Ca2+, Zn2+, Lu3+, Y3+ and Sc3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca2+ and Sr2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities of complexes formed with stronger Lewis acidities were found to be markedly different. In conclusion, complexes that contain Ca2+ or Sr2+ ions were oxidized by an electron acceptor to release O2, whereas the release of O2 did not occur for complexes that bind stronger Lewis acids. Furthermore, we discuss these results in the light of the functional role of the Ca2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH); KOSEF/MEST of Korea
Grant/Contract Number:
NRF-2012R1A3A2048842; NRF-2010-00353; 2013R1A1A2062737; P41 RR001209
OSTI ID:
1291342
Journal Information:
Nature Chemistry, Vol. 6, Issue 10; ISSN 1755-4330
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 119 works
Citation information provided by
Web of Science

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Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO 2 Reduction journal August 2019
Molecular Engineering of a 3D Self‐Supported Electrode for Oxygen Electrocatalysis in Neutral Media journal November 2019
A Heterobimetallic Superoxide Complex formed through O 2 Activation between Chromium(II) and a Lithium Cation journal December 2014
Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO 2 Reduction journal September 2019
Molecular Engineering of a 3D Self‐Supported Electrode for Oxygen Electrocatalysis in Neutral Media journal December 2019
Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex journal May 2020
Homogeneous and Heterogeneous Photocatalytic Water Oxidation by Persulfate journal February 2016
Lewis Acid Coupled Electron Transfer of Metal-Oxygen Intermediates journal September 2015
The Influence of Alkali Metal Ions on the Stability and Reactivity of Chromium(III) Superoxide Moieties Spanned by Siloxide Ligands journal March 2019
Generation and Electron‐Transfer Reactivity of the Long‐Lived Photoexcited State of a Manganese(IV)‐Oxo‐Scandium Nitrate Complex journal January 2020
How calcium affects oxygen formation journal September 2014
Synthesis of carboxylate-bridged iron–thiolate clusters from alcohols/aldehydes or carboxylate salts journal January 2015
Heterotrimetallic sandwich complexes supported by sulfonamido ligands journal January 2016
Electrocatalytic water oxidation by a macrocyclic Cu( ii ) complex in neutral phosphate buffer journal January 2016
Stereochemistry of metal tetramethylcyclam complexes directed by an unexpected anion effect journal January 2017
Unusual undecanuclear heterobimetallic Zn 4 Ln 7 (Ln = Gd, Dy) nano-sized clusters encapsulating two peroxide anions through spontaneous intake of dioxygen journal January 2017
Incorporation of redox-inactive cations promotes iron catalyzed aerobic C–H oxidation at mild potentials journal January 2018
Kinetics and mechanisms of catalytic water oxidation journal January 2019
Significantly improved electrocatalytic oxygen reduction by an asymmetrical Pacman dinuclear cobalt( ii ) porphyrin–porphyrin dyad journal January 2020
In situ formation of molecular Ni-Fe active sites on heteroatom-doped graphene as a heterogeneous electrocatalyst toward oxygen evolution journal March 2018
Preface — Special Issue in Honor of Professor Shunichi Fukuzumi journal January 2015
An Examination of the Electron Densities in a Series of Tripodal Cobalt Complexes Bridged by Magnesium, Calcium, Strontium, and Barium † journal May 2018
An Examination of the Electron Densities in a Series of Tripodal Cobalt Complexes Bridged by Magnesium, Calcium, Strontium and Bariumíííííí posted_content May 2018
Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex journal May 2020
Lewis versus Brønsted Acid Activation of a Mn(IV) Catalyst for Alkene Oxidation journal October 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
redox-inactive metal ions