Manganese(III) Nitrate Complexes as Bench-Stable Powerful Oxidants

We report herein a convenient one-pot synthesis for the shelf-stable molecular complex [Mn(NO₃)₃(OPPh₃)₂] (2) and describe the properties that make it a powerful and selective one-electron oxidation (deelectronation) reagent. 2 has a high reduction potential of 1.02 V versus ferrocene (MeCN) (1.65 vs normal hydrogen electrode), which is one the highest known among readily available redox agents used in chemical synthesis. 2 exhibits stability toward air in the solid state, can be handled with relative ease, and is soluble in most common laboratory solvents such as MeCN, dichloromethane, and fluorobenzene. 2 is substitutionally labile with respect to the coordinated (pseudo)halide ions enabling the synthesis of other new Mn(III) nitrato complexes also with high reduction potentials ranging from 0.6 to 1.0 V versus ferrocene.