Intermediates for Biological and Synthetic Manganese Catalysts

In biology, enzymes that use the transition metal manganese are capable of an amazing range of reactions. The versatility of these reactions can be explained, in part, by the ability of manganese to react with molecular oxygen (O2) and all of its reduced derivatives- superoxide (O2-), hydrogen peroxide (H2O2), and water (H2O). One example of a critically important manganese-containing enzyme that we are trying to understand is the oxygen-evolving center of photosystem II. This enzyme uses a tetramanganese active site to convert water to molecular oxygen, a critical reaction for photosysnthesis. Gaining an understanding of the elementary steps in this process has relevance towards finding accessible energy for today’s world. Another important reaction catalyzed by manganese-dependent enzymes is the conversion of nucleotides to deoxynucleotides by Mn-dependent ribonucleotide reductase. Manganese superoxide dismutase (SOD), which is responsible for detoxifying superoxide, is another example of a vital function that is dependent on manganese. These and other examples are shown in the scheme below.

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While many of these biological processes are have been and are currently being investigated by chemists, biochemists, and molecular biologists, there remains ambiguity about the mechanisms, in particular the interaction between molecular oxygen and its derivatives and the active-site manganese centers. While oxomanganese adducts are commonly accepted as being responsible for oxidation in many biological processes, several manganese-hydroxo adducts are also capable of these oxidations (such is the case the Mn-lipoxygenase). However, the processes that govern the selection of one of these oxidants by metalloenzymes are not well understood. In addition, peroxomanganese species are proposed as intermediates in the catalytic cycles of many manganese-dependent enzymes.

Oxo- and peroxomanganese intermediates also feature prominently in the catalytic cycles of synthetic Mn complexes that serve as oxidation catalysts. The advantages of these catalysts (i.e., low expense and toxicity) are tempered by efficiencies and selectivities lower than state-of-the art systems that rely on expensive precious metal catalysts, stoichiometric oxidants, and/or toxic reagents. By developing structure-function relationships for oxo- and peroxomanganese intermediates, we intend to uncover principles that would lead to the design of more efficient catalysts.

We are currently performing systematic studies of the geometric, electronic, and reactivity properties of a series of peroxomanganese(III) adducts (MnIII-O2) generated in our lab. Our initial paper on MnIII-O2 adducts ( was the first to use MCD spectroscopy, which, when combined with electronic absorption data and DFT computations, allowed us to conclude that the electronic properties of the supporting ligand strongly influence the Mn-O(peroxo) bond length. This work thus provides new insights into how protein active sites could modulate Mn-O2 interactions. Our current work involves investigating how more diverse functional groups affect Mn-O2 interactions, as well as exploring the consequences of steric and electronic properties on reactivity.

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In collaboration with Prof. Daryle Busch (Department of Chemistry, University of Kansas), we have compared the geometric and electronic structures of a pair of bis(hydroxo)- and oxohydroxomanganese(IV) complexes that differ only by a proton. This pair is thus ideally suited for understanding the differences and similarities between oxo- and hydroxometal oxidants, a subject of emerging interest. Our collaborative investigation of MnIV=O and MnIVOH adducts used spectroscopic data to directly compare p- and s-bonding in these complexes, and suggested that the modest difference in reactivity reported for these complexes is due to steric effects ( To gain further insights into the differences between oxo- and hydroxometal species, we are currently performing DFT calculations to determine why the MnIV=O and MnIVOH adducts oxidize hydrocarbons to give different products.

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Jackson Group News
December 2019
Welcome to the group, Helena Howell!
August 2019
Steric control of dixoygen activation pathways for MnII complexes supported by pentadentate, amide-containing ligands by Joshua Parham, Gayan Wijeratne, and Jaycee Mayfield in Dalton Transactions
May 2019
Congratulations to Eleanor Stewart-Jones, receiving the Barry M. Goldwater Scholarship!
March 2019
MnIV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for MnIV-oxo than FeIV-oxo species by Melissa Denler, Allyssa Massie, and Eleanor Stewart-Jones In Dalton Transactions
December 2018
Welcome to the group, Samuel Crowell and Priya Singh!
September 2018
MnIII-Peroxo adduct supported by a new tetradentate ligand shows acid-sensitive aldehyde deformylation reactivity by Melissa Denler, Gayan Wijeratne, Derek Rice, and Hannah Colmer In Dalton Transactions
May 2018
Congratulations to Allyssa Massie and Derek Rice, graduating with Ph.D with honors!
March 2018
ACS National meeting in New Orleans by Melissa Denler and Yuri Lee.
February 2018
Spectroscopic and Structural Characterization of Mn(III)-Alkylperoxo Complexes Supported by Pentadentate Amide-Containing Ligands by Joshua Parham, Gayan Wijeratne, and Derek Rice In Inorganic Chemistry
December 2017
Mn K-edge X-ray absorption studies of mononuclear Mn(III)-hydroxo complexes by Derek Rice and Gayan Wijeratne in Journal of Biological Inorganic Chemistry
Welcome to the group, Jaycee Mayfield and Elizabeth Grotemeyer!
October 2017 
Manganese-oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions by Derek Rice and Allyssa Massie in Accounts of Chemical Research
April 2017
ACS National meeting in San Francisco by Derek Rice, Allyssa Massie, Melissa Denler, Joshua Parham, and Aruna Munasinghe.
March 2017
Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes by Allyssa Massie, Melissa Denler, et. al in Angewandte Chemi International Edition
December 2016
Welcome to the group, Yuri Lee!
November 2016
July 2016
Steric and Electronic Influence on Proton-Coupled Electron-Transfer Reactivity of a Mononuclear Mn(III)-Hydroxo Complex by Derek Rice, Gayan Wijeratne, Andrew Burr, and Josh Parham in Inorganic Chemistry
April 2016
Congratulations to Hannah Colmer, graduating with Ph.D with honors!
December 2015
Welcome to the group, Aruna Munasinghe!
June 2015
Welcome to the group, Melissa Denler!
June 2015
Congratulations to Gayan Wijeratne, graduating with Ph.D. with honors!
April 2015
Presentation by Gayan Wijeratne, "Dioxygen activation under ambient conditions using bio-inspired manganese(II) complexes to generate mid-valent oxidants for catalytic O–H bond oxidations," and poster presentation by Hannah Colmer, "Formation, Characterization, and O-O Bond Activation of a Bio-inspired Peroxomanganese(III) Complex," at 249th ACS National Meeting and Exposition, Denver, CO.
January 2015
"O–H bond oxidation by a monomeric Mn(III)–OMe complex" by Gayan Wijeratne published in Dalton Transactions
December 2014
Welcome to the group, Josh Parham!
November 2014
October 2014
July 2014

"Saturation Kinetics in Phenolic O–H Bond Oxidation by a Mononuclear Mn(III)–OH Complex Derived from Dioxygen" by Gayan Wijeratne and Briana Corzine published in Inorganic Chemistry

June 2014
June 2014
Domenick Leto graduates with Ph.D with honors
May 2014
January 2014
Poster presentation by Dr. Timothy Jackson at the Metals in Biology Gordon Research Conference and by Domenick Leto, Gayan Wijeratne, and Hannah Colmer at the Bioinorganic Gordon Research Seminar in Ventura, CA
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