Synthesis and Characterization of Manganese and Iron Complexes

Unless otherwise specified, all compounds were manipulated using a glovebox or standard Schlenk line techniques with an N₂ atmosphere. Anhydrous tetrahydrofuran (THF) was purchased from Aldrich in 18 L Pure-Pac™ containers. Anhydrous benzene, dichloromethane, and diethyl ether were purified by sparging with nitrogen for 15 minutes and then passing under nitrogen pressure through a column of activated A2 alumina (Zapp’s). Methylene chloride-d₂ and acetonitrile-d₃ were purchased from Cambridge Isotopes, dried over calcium hydride, and vacuum transferred prior to use. Benzene-d₆ was also purchased from Cambridge Isotope Laboratories, Inc., dried over sodium/benzophenone ketyl, and vacuum transferred prior to use. Unless indicated otherwise, all commercial chemicals were used as received. LMn₃(OAc)₃,^{52 (link)}[Mn^IV₃ScO₄],^{40 (link)}[Mn^IV₃GdO₄],^{39 (link)}[Mn^IIIMn^IV₂GdO₄],^{39 (link)}[Mn^III₃CaO(OH)], [Mn^IIMn^III₂YO(OH)], [Mn^IIMn^III₂CaO(OH)],^{43 (link)}[Fe^III₃LaO(OH)], [Fe^III₃CaO(OH)], [Fe^IIFe^III₂ScO(OH)], [Fe^IIFe^III₂LaO(OH)], and [Fe^IIFe^III₂CaO(OH)]^{42 (link)} were prepared according to previously published protocols. ¹H and ³¹P NMR spectra were recorded on a Varian Mercury 300 spectrometer at room temperature. Elemental analyses were performed by Robertson Microlit Laboratories, Ledgewood, NJ.