title: Oxidative atom-transfer to a trimanganese complex to form Mn6(μ6-E) (E = O, N) clusters featuring interstitial oxide and nitride functionalities.
abstract: Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ((H)L)Mn(3)(thf)(3) was synthesized and characterized ([(H)L](6-) = [MeC(CH(2)N(C(6)H(4)-o-NH))(3)](6-)). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ(6)-oxo complex ((H)L)(2)Mn(6)(μ(6)-O)(NCMe)(4), where two trinuclear subunits bind the central O-atom and the ((H)L) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ((H)L)Mn(3)(thf)(3) rapidly consumes inorganic azide ([N(3)]NBu(4)) to afford a dianionic hexanuclear nitride complex [((H)L)(2)Mn(6)(μ(6)-N)](NBu(4))(2), which subsequently can be oxidized with elemental iodine to ((H)L)(2)Mn(6)(μ(6)-N)(NCMe)(4). EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge Massachusetts 02138, USA.
authors.forename: Alison R
authors.initials: AR
authors.lastname: Fout
authors.forename: Qinliang
authors.initials: Q
authors.lastname: Zhao
authors.forename: Dianne J
authors.initials: DJ
authors.lastname: Xiao
authors.forename: Theodore A
authors.initials: TA
authors.lastname: Betley
mesh_terms: D008345:Manganese / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D010087:Oxides; D008345:Manganese; D009584:Nitrogen; D010100:Oxygen