A manganese oxido complex bearing facially coordinating trispyridyl ligands – is coordination geometry crucial for water oxidation catalysis??

Dalton Transactions Pub Date: 2012-03-12 DOI: 10.1039/C2DT30129F

Abstract

In this work the synthesis of the novel manganese complex [Mn2III,III(tpdm)2(μ-O)(μ-OAc)2]2+ (1) is reported, containing two manganese centres ligated to the unusual, facially coordinating, all-pyridine ligand tpdm (tris(2-pyridyl)methane). The geometric and electronic properties of complex 1 were characterised by X-ray crystallography, vibrational (IR and Raman) and optical spectroscopy (UV/Vis and MCD). Cyclic voltammograms of 1 showed a quasi-reversible oxidation event at 950 mV and an irreversible reduction wave at ?250 mV vs. Ag/Ag+. The redox behaviour of the compound was investigated in detail by UV/Vis- and X-band EPR-spectroelectrochemistry. Both electrochemical (+1200 mV) and chemical (tBuOOH) oxidations transform 1 into the singly oxidized di-μ-oxido species [Mn2III,IV(tpdm)2(μ-O)2(μ-OAc)]2+. Further electrochemical oxidation at the same potential results in the removal of a second electron to obtain a Mn2IV,IV-species. The ability of compound 1 to evolve O2 was studied using different reaction agents. While reactions with both hydrogen peroxide and peroxomonosulfate yield O2, homogeneous water-oxidation using CeIV was not observed. Nevertheless, the oxidation reactions of 1 are very interesting model processes for oxidation state (S-state) transitions of the natural manganese water-oxidation catalyst in photosynthesis. However, despite its favourable coordination geometry and multielectron redox chemistry, complex 1 fails to be a catalytically active model for natural water-oxidation.

Graphical abstract: A manganese oxido complex bearing facially coordinating trispyridyl ligands – is coordination geometry crucial for water oxidation catalysis?
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