title: Helicity inversion and redox chemistry of chiral manganese(II) cubanes.
abstract: The chiral ligand S-1,2-bis(1H-benzimidazol-2-yl)ethanol, 1, reacts with manganese(II) salts to form cubanes which readily undergo oxidation reactions leading either to a tetranuclear manganese(II,III) mixed valence complex 4 or to a tetranuclear complex of ligand 5 where the secondary alcohol has been oxidised to an enolate. N-methylation of ligand 1 slows the oxidation reaction and stable manganese(II) cubanes may be isolated. The fully methylated ligand 2 gives a cubane of opposite helicity to that found previously for 1 with cobalt. The inversion may be explained by conformational analysis. Cyclic voltammetry suggests that the manganese cubanes reported here are insufficiently robust to store oxidising equivalents as in the oxygen evolving system of photosystem II.
authors.affiliation: Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai Ernest Ansermet, CH 1211 Geneva 4, Switzerland. Alan.Willliams@unige.ch.
authors.forename: Claire
authors.initials: C
authors.lastname: Deville
authors.forename: Matteo
authors.initials: M
authors.lastname: Granelli
authors.forename: Alan M
authors.initials: AM
authors.lastname: Downward
authors.forename: Céline
authors.initials: C
authors.lastname: Besnard
authors.forename: Laure
authors.initials: L
authors.lastname: Guenée
authors.forename: Alan F
authors.initials: AF
authors.lastname: Williams