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Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2];  [2];  [3];  [2];  [3];  [2]
  1. Univ. of Kansas, Lawrence, KS (United States); DOE/OSTI
  2. Univ. of Kansas, Lawrence, KS (United States)
  3. Lund Univ. (Sweden)
+ Show Author Affiliations

Manganese(IV)-oxo complexes are often invoked as intermediates in Mn-catalyzed C–H bond activation reactions. While many synthetic MnIV-oxo species are mild oxidants, other members of this class can attack strong C–H bonds. The basis for these reactivity differences is not well understood. In this work, we describe a series of MnIV-oxo complexes with N5 pentadentate ligands that modulate the equatorial ligand field of the MnIV center, as assessed by electronic absorption, electron paramagnetic resonance, and Mn K-edge X-ray absorption methods. Kinetic experiments show dramatic rate variations in hydrogen-atom and oxygen-atom transfer reactions, with faster rates corresponding to weaker equatorial ligand fields. For these MnIV-oxo complexes, the rate enhancements are correlated with both 1) the energy of a low-lying 4E excited state, which has been postulated to be involved in a two-state reactivity model, and 2) the MnIII/IV reduction potentials.

Research Organization:
Univ. of Kansas, Lawrence, KS (United States); Stanford Univ., CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Organization:
USDOE Office of Science (SC); National Institutes of Health (NIH); Ciências sem Fronteiras; National Science Foundation (NSF); European Commission
Grant/Contract Number:
SC0016359; AC02-76SF00515; SC0012704
OSTI ID:
1533097
Alternate ID(s):
OSTI ID: 1401075
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 15 Vol. 56; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (12)

Oxidation of Naphthalene with a Manganese(IV) Bis(hydroxo) Complex in the Presence of Acid journal May 2018
Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant journal June 2018
Oxidation of Naphthalene with a Manganese(IV) Bis(hydroxo) Complex in the Presence of Acid journal May 2018
Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant journal June 2018
Structural Characterization of a Series of N5‐Ligated Mn IV ‐Oxo Species journal September 2019
Ligand Influence on Structural Properties and Reactivity of Bis(μ-oxo)dimanganese(III,IV) Species and Comparison of Reactivity with Terminal Mn IV -oxo Complexes journal December 2018
Dramatic rate-enhancement of oxygen atom transfer by an iron( iv )-oxo species by equatorial ligand field perturbations journal January 2018
Synthesis, characterization, and reactivity of a chiral Fe( iv )–oxo complex bearing an l -proline-derived aminopyridine ligand journal January 2018
Selective C–H halogenation over hydroxylation by non-heme iron( iv )-oxo journal January 2018
Mn IV -Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn IV -oxo than Fe IV -oxo species journal January 2019
Steric control of dioxygen activation pathways for Mn II complexes supported by pentadentate, amide-containing ligands journal January 2019
Formation, stability and catalase-like activity of mononuclear manganese( ii ) and oxomanganese( iv ) complexes in protic and aprotic solvents journal January 2020

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Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)‐Oxo Complexes
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C-H activation
chemistry
hydrogen atom transfer
kinetics
manganese
metal oxo compounds