Tuning the Relative Stability and Reactivity of Manganese Dioxygen and Peroxo Intermediates via Systematic Ligand Modification

Accounts of Chemical Research
Julie A Kovacs

Abstract

Many fundamental processes of life depend on the chemical energy stored in the O–O bond of dioxygen (O2), the majority of which is derived from photosynthetic H2O oxidation. Key steps in these processes involve Mn-, Fe-, or Cu-promoted formation or cleavage of O–O and O–H bonds, the mechanisms of which are not fully understood, especially with Mn. Metal–peroxo and high-valent metal–oxo species are proposed to be involved as intermediates. The metal ion properties that favor O–O and O–H bond formation versus cleavage have yet to be systematically explored. Herein we examine the O2 reactivity of a series of structurally related Mn(II) complexes and show that several metastable intermediates are observed, the relative stabilities of which depend on subtle differences in ligand architecture. We show that in contrast to Fe and Cu complexes, O2 binds irreversibly to Mn(II). By crystallizing an entire series of the first reported examples of Mn(III)–OOR peroxos as well as an O2-derived binuclear trans-μ-1,2-bridged Mn(III)–peroxo with varying degrees of O–O bond activation, we demonstrate that there are distinct correlations between spectroscopic, structural, and reactivity properties. Rate-limiting O–O bond cleavage is shown to affor...Continue Reading

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Citations

Sep 1, 2016·Journal of the American Chemical Society·Sumit Sahu, David P Goldberg
Nov 18, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Adam T Fiedler, Anne A Fischer
Oct 17, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Claudio SaraciniWonwoo Nam
Apr 4, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Chien-Ming LeeWonwoo Nam
Apr 13, 2019·Angewandte Chemie·Tomasz PietrzakJanusz Lewiński
Jan 10, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Sruti MondalSanjib Kar
Jul 21, 2020·Chemical Communications : Chem Comm·Bongki ShinJaeheung Cho
Oct 17, 2017·Chemical Communications : Chem Comm·Teresa CoronaAnna Company
Jul 26, 2019·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Maksym A DedushkoJulie A Kovacs
May 22, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Shunichi FukuzumiWonwoo Nam
Apr 15, 2021·Journal of the American Chemical Society·Alexandra N DowningJulie A Kovacs
Jun 24, 2021·Journal of the American Chemical Society·Zhiliang HuangJianliang Xiao
Sep 5, 2019·Journal of the American Chemical Society·Penny Chaau Yan PoonJulie A Kovacs
Oct 24, 2017·Journal of the American Chemical Society·Mian GuoWonwoo Nam
Dec 16, 2020·Journal of the American Chemical Society·Norman ZhaoJohn S Anderson
Jul 20, 2018·Inorganic Chemistry·Feng JiangElisabeth Bouwman
Aug 23, 2018·Inorganic Chemistry·Claudio SaraciniShunichi Fukuzumi
Dec 30, 2016·Journal of the American Chemical Society·Gloria Villar-AcevedoJulie A Kovacs
Jun 30, 2019·Journal of the American Chemical Society·Zhenlian ChenXiao Cheng Zeng
Sep 9, 2021·Journal of the American Chemical Society·Adedamola A OpaladeTimothy A Jackson
Nov 4, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Emma N Cook, Charles W Machan

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