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Equatorial Ligand P...
Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes
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- Massie, Allyssa A. (author)
- University of Kansas
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- Denler, Melissa C. (author)
- University of Kansas
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- Cardoso, Luísa Thiara (author)
- University of Kansas
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- Walker, Ashlie N. (author)
- University of Kansas
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- Hossain, Kamal (author)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Day, Victor W. (author)
- University of Kansas
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- Nordlander, Ebbe (author)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Jackson, Timothy A. (author)
- University of Kansas
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(creator_code:org_t)
- 2017-03-16
- 2017
- English.
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In: Angewandte Chemie (International edition). - : Wiley. - 1433-7851. ; 56:15, s. 4178-4182
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Abstract
Subject headings
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- 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. Here 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.
Subject headings
- NATURVETENSKAP -- Kemi -- Materialkemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Materials Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
Keyword
- C-H activation
- Hydrogen atom transfer
- Kinetics
- Manganese
- Metal-oxo compounds
Publication and Content Type
- art (subject category)
- ref (subject category)
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