Hydroxide ion versus chloride and methoxide as an exogenous ligand reveals the influence of hydrogen bonding with second-sphere coordination water molecules in the electron transfer kinetics of Mn complexes |
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Authors: | El Ghachtouli Sanae Guillot Régis Aukauloo Ally Dorlet Pierre Anxolabéhère-Mallart Elodie Costentin Cyrille |
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Affiliation: | Laboratoire d'Electrochimie Moléculaire, Univ Paris Diderot, Sorbonne Paris Cité, Unité Mixte de Recherche Université-CNRS No. 7591, Batiment Lavoisier, 15 rue Jean de Ba?f, 75205 Paris Cedex 13, France. |
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Abstract: | We recently reported on the synthesis of a new pentadentate N(4)O ligand, tBuL(-), together with the X-ray diffraction structure of the corresponding mononuclear manganese(III)-hydroxo complex namely [(tBuL)Mn(III)OH](ClO(4)), (1 (ClO(4))). [El Ghachtouli et al. Energy Environ. Sci. 2011, 4, 2041.] In the present work, we evidence through electrochemical analysis that complex 1(+), in the presence of water, shows a peculiar behavior toward electron-transfer kinetics. The synthesis, single-crystal X-ray diffraction, and EPR spectroscopic characterization of two other mononuclear manganese(III)-chlorido and methoxo complexes-namely, [(tBuL)Mn(III)Cl](PF(6)), (2(PF(6))) and [(tBuL)Mn(III)OMe](ClO(4)), (3(ClO(4)))-are also reported. 2(PF(6)) and 3(ClO(4)) compounds will serve as reference complexes for the electron-transfer kinetics investigation. The peculiar behavior of 1(ClO(4)) is attributed to the specificity of hydroxide anion as ligand presumably allowing intermolecular hydrogen-bonding interactions and thus affecting electron-transfer properties. |
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