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

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.

Denler, Melissa C.University of Kansas (författare)
Cardoso, Luísa ThiaraUniversity of Kansas (författare)
Walker, Ashlie N.University of Kansas (författare)
Hossain, KamalLund 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(Swepub:lu)chem-kmh (författare)
Day, Victor W.University of Kansas (författare)
Nordlander, EbbeLund 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(Swepub:lu)ook1-eno (författare)
Jackson, Timothy A.University of Kansas (författare)
University of KansasKemisk fysik (creator_code:org_t)

Ingår i:Angewandte Chemie (International edition): Wiley56:15, s. 4178-41821433-7851
Ingår i:Angewandte Chemie International Edition: Wiley56:15, s. 4178-41821521-3773

Av författaren/redakt...: Massie, Allyssa ...; Denler, Melissa ...; Cardoso, Luísa T ...; Walker, Ashlie N ...; Hossain, Kamal; Day, Victor W.; visa fler...; Nordlander, Ebbe; Jackson, Timothy ...; visa färre...

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