Abstract
The new complex [Mn(bipyalk)(H2O)(µ-O)]2(OTf)2 {bipyalk = 2-([2,2′-bipyridin]-6-yl)propan-2-olate} catalyzes oxygen evolution with a TOF of 0.0055 s–1 when driven by the sacrificial oxidant KHSO5 in water. It is proposed on the basis of EPR experiments that the catalyst proceeds through a MnV(µ-O)2MnV=O intermediate supported by the highly donating tertiary alkoxide moiety of the ligand. The Mn(IV,IV) dimer can also be formed electrochemically from its precursor, Mn(bipyalkH)Cl2. A related series of bis-ligated monomers of the type [Mnn(bipyalkHx)(bipyalkHy)](PF6)2 is also reported, where the dication features MnII, MnIII, and MnIV oxidation states and corresponding protonation states. Electrochemical data on this series underscore the importance of proton loss at the alcohol/alkoxide moiety during oxidation to maintain low overpotentials required for catalysis.
| Original language | English |
|---|---|
| Journal | European Journal of Inorganic Chemistry |
| DOIs | |
| Publication status | Published - Jan 1 2019 |
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Keywords
- High oxidation state
- Homogeneous catalysis
- Manganese
- Oxygen evolution
- Water splitting
ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox-Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution. / Lant, Hannah M.C.; Michaelos, Thoe K.; Sharninghausen, Liam S.; Mercado, Brandon Q.; Crabtree, Robert H.; Brudvig, Gary W.
In: European Journal of Inorganic Chemistry, 01.01.2019.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox-Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution
AU - Lant, Hannah M.C.
AU - Michaelos, Thoe K.
AU - Sharninghausen, Liam S.
AU - Mercado, Brandon Q.
AU - Crabtree, Robert H.
AU - Brudvig, Gary W
PY - 2019/1/1
Y1 - 2019/1/1
N2 - The new complex [Mn(bipyalk)(H2O)(µ-O)]2(OTf)2 {bipyalk = 2-([2,2′-bipyridin]-6-yl)propan-2-olate} catalyzes oxygen evolution with a TOF of 0.0055 s–1 when driven by the sacrificial oxidant KHSO5 in water. It is proposed on the basis of EPR experiments that the catalyst proceeds through a MnV(µ-O)2MnV=O intermediate supported by the highly donating tertiary alkoxide moiety of the ligand. The Mn(IV,IV) dimer can also be formed electrochemically from its precursor, Mn(bipyalkH)Cl2. A related series of bis-ligated monomers of the type [Mnn(bipyalkHx)(bipyalkHy)](PF6)2 is also reported, where the dication features MnII, MnIII, and MnIV oxidation states and corresponding protonation states. Electrochemical data on this series underscore the importance of proton loss at the alcohol/alkoxide moiety during oxidation to maintain low overpotentials required for catalysis.
AB - The new complex [Mn(bipyalk)(H2O)(µ-O)]2(OTf)2 {bipyalk = 2-([2,2′-bipyridin]-6-yl)propan-2-olate} catalyzes oxygen evolution with a TOF of 0.0055 s–1 when driven by the sacrificial oxidant KHSO5 in water. It is proposed on the basis of EPR experiments that the catalyst proceeds through a MnV(µ-O)2MnV=O intermediate supported by the highly donating tertiary alkoxide moiety of the ligand. The Mn(IV,IV) dimer can also be formed electrochemically from its precursor, Mn(bipyalkH)Cl2. A related series of bis-ligated monomers of the type [Mnn(bipyalkHx)(bipyalkHy)](PF6)2 is also reported, where the dication features MnII, MnIII, and MnIV oxidation states and corresponding protonation states. Electrochemical data on this series underscore the importance of proton loss at the alcohol/alkoxide moiety during oxidation to maintain low overpotentials required for catalysis.
KW - High oxidation state
KW - Homogeneous catalysis
KW - Manganese
KW - Oxygen evolution
KW - Water splitting
UR - http://www.scopus.com/inward/record.url?scp=85061011004&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85061011004&partnerID=8YFLogxK
U2 - 10.1002/ejic.201801343
DO - 10.1002/ejic.201801343
M3 - Article
JO - Chemische Berichte
JF - Chemische Berichte
SN - 0009-2940
ER -