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

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 41; no. 20; pp. 6215 - 6224
• Main Authors: Berends, Hans-Martin, Manke, Anne-Marie, Näther, Christian, Tuczek, Felix, Kurz, Philipp
• Format: Journal Article
• Language: English
• Published: England 28.05.2012
• Subjects: Catalysis; Catalysts; Crystallography, X-Ray; Dimerization; Electrochemistry; Ligands; Manganese; Manganese - chemistry; Organometallic Compounds - chemistry; Oxidation; Oxidation-Reduction; Oxygen - chemistry; Photosynthesis; Pyridines - chemistry; Reduction; Spectrum Analysis; Water - chemistry; X-band
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt30129f

In this work the synthesis of the novel manganese complex [Mn(2)(III,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 [Mn(2)(III,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 Mn(2)(IV,IV)-species. The ability of compound 1 to evolve O(2) was studied using different reaction agents. While reactions with both hydrogen peroxide and peroxomonosulfate yield O(2), homogeneous water-oxidation using Ce(IV) 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.