An anionic N-donor ligand promotes manganese-catalyzed water oxidation

Karin J. Young, Michael K. Takase, Gary W Brudvig

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

Four manganese complexes of pentadentate ligands have been studied for their ability to act as oxygen evolution catalysts in the presence of Oxone or hydrogen peroxide. The complexes [Mn(PaPy3)(NO3)](ClO 4) (1) (PaPy3H = N,N-bis(2-pyridylmethyl)-amine-N-ethyl-2- pyridine-2-carboxamide) and [Mn(PaPy3)(μ-O)(PaPy 3)Mn](ClO4)2 (2) feature an anionic carboxamido ligand trans to the labile sixth coordination site, while [Mn(N4Py)OTf](OTf) (3) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and [Mn(PY5)(OH2)](ClO4)2 (4) (PY5 = 2,6-bis(bis(2-pyridyl)methoxymethane)-pyridine) have neutral ligands of varying flexibility. 1 and 2 are shown to evolve oxygen in the presence of either Oxone or hydrogen peroxide, but 3 evolves oxygen only in the presence of hydrogen peroxide. 4 is inactive. The activity of 1 and 2 with Oxone suggests that the presence of an anionic N-donor ligand plays a role in stabilizing putative high-valent intermediates. Anionic N-donor ligands may be viewed as alternatives to μ-oxo ligands that are prone to protonation in low-valent Mn species formed during a catalytic cycle, resulting in loss of catalyst structure.

Original languageEnglish
Pages (from-to)7615-7622
Number of pages8
JournalInorganic Chemistry
Volume52
Issue number13
DOIs
Publication statusPublished - Jul 1 2013

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Manganese
manganese
Ligands
Oxidation
ligands
oxidation
Water
hydrogen peroxide
Hydrogen Peroxide
water
peroxides
Oxygen
pyridines
oxygen
catalysts
Catalysts
Protonation
amines
flexibility
cycles

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

An anionic N-donor ligand promotes manganese-catalyzed water oxidation. / Young, Karin J.; Takase, Michael K.; Brudvig, Gary W.

In: Inorganic Chemistry, Vol. 52, No. 13, 01.07.2013, p. 7615-7622.

Research output: Contribution to journalArticle

Young, Karin J. ; Takase, Michael K. ; Brudvig, Gary W. / An anionic N-donor ligand promotes manganese-catalyzed water oxidation. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 13. pp. 7615-7622.
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abstract = "Four manganese complexes of pentadentate ligands have been studied for their ability to act as oxygen evolution catalysts in the presence of Oxone or hydrogen peroxide. The complexes [Mn(PaPy3)(NO3)](ClO 4) (1) (PaPy3H = N,N-bis(2-pyridylmethyl)-amine-N-ethyl-2- pyridine-2-carboxamide) and [Mn(PaPy3)(μ-O)(PaPy 3)Mn](ClO4)2 (2) feature an anionic carboxamido ligand trans to the labile sixth coordination site, while [Mn(N4Py)OTf](OTf) (3) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and [Mn(PY5)(OH2)](ClO4)2 (4) (PY5 = 2,6-bis(bis(2-pyridyl)methoxymethane)-pyridine) have neutral ligands of varying flexibility. 1 and 2 are shown to evolve oxygen in the presence of either Oxone or hydrogen peroxide, but 3 evolves oxygen only in the presence of hydrogen peroxide. 4 is inactive. The activity of 1 and 2 with Oxone suggests that the presence of an anionic N-donor ligand plays a role in stabilizing putative high-valent intermediates. Anionic N-donor ligands may be viewed as alternatives to μ-oxo ligands that are prone to protonation in low-valent Mn species formed during a catalytic cycle, resulting in loss of catalyst structure.",
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