title: Reactivity and O2 Formation by Mn(IV)- and Mn(V)-Hydroxo Species Stabilized within a Polyfluoroxometalate Framework.
abstract: Manganese(IV,V)-hydroxo and oxo complexes are often implicated in both catalytic oxygenation and water oxidation reactions. Much of the research in this area is designed to structurally and/or functionally mimic enzymes. On the other hand, the tendency of such mimics to decompose under strong oxidizing conditions makes the use of molecular inorganic oxide clusters an enticing alternative for practical applications. In this context it is important to understand the reactivity of conceivable reactive intermediates in such an oxide-based chemical environment. Herein, a polyfluoroxometalate (PFOM) monosubstituted with manganese, [NaH2(Mn-L)W17F6O55](q-), has allowed the isolation of a series of compounds, Mn(II, III, IV and V), within the PFOM framework. Magnetic susceptibility measurements show that all the compounds are high spin. XPS and XANES measurements confirmed the assigned oxidation states. EXAFS measurements indicate that Mn(II)PFOM and Mn(III)PFOM have terminal aqua ligands and Mn(V)PFOM has a terminal hydroxo ligand. The data are more ambiguous for Mn(IV)PFOM where both terminal aqua and hydroxo ligands can be rationalized, but the reactivity observed more likely supports a formulation of Mn(IV)PFOM as having a terminal hydroxo ligand. Reactivity studies in water showed unexpectedly that both Mn(IV)-OH-PFOM and Mn(V)-OH-PFOM are very poor oxygen-atom donors; however, both are highly reactive in electron transfer oxidations such as the oxidation of 3-mercaptopropionic acid to the corresponding disulfide. The Mn(IV)-OH-PFOM compound reacted in water to form O2, while Mn(V)-OH-PFOM was surprisingly indefinitely stable. It was observed that addition of alkali cations (K(+), Rb(+), and Cs(+)) led to the aggregation of Mn(IV)-OH-PFOM as analyzed by electron microscopy and DOSY NMR, while addition of Li(+) and Na(+) did not lead to aggregates. Aggregation leads to a lowering of the entropic barrier of the reaction without changing the free energy barrier. The observation that O2 formation is fastest in the presence of Cs(+) and ∼fourth order in Mn(IV)-OH-PFOM supports a notion of a tetramolecular Mn(IV)-hydroxo intermediate that is viable for O2 formation in an oxide-based chemical environment. A bimolecular reaction mechanism involving a Mn(IV)-hydroxo based intermediate appears to be slower for O2 formation.
authors.affiliation: †Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel.
authors.forename: Roy E
authors.initials: RE
authors.lastname: Schreiber
authors.affiliation: ‡Department for Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel.
authors.forename: Hagai
authors.initials: H
authors.lastname: Cohen
authors.affiliation: ‡Department for Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel.
authors.forename: Gregory
authors.initials: G
authors.lastname: Leitus
authors.affiliation: ‡Department for Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel.
authors.forename: Sharon G
authors.initials: SG
authors.lastname: Wolf
authors.affiliation: §Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, United States.
authors.forename: Ang
authors.initials: A
authors.lastname: Zhou
authors.affiliation: §Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, United States.
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
authors.affiliation: †Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel.
authors.forename: Ronny
authors.initials: R
authors.lastname: Neumann
mesh_terms: D054879:Halogenation; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D017973:Tungsten Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D008345:Manganese; D010100:Oxygen; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates