An isolable, nonreducible high-valent manganese(V) imido corrolazine complex.

The manganese(V) imido complex [(TBP8Cz)Mn(V)(NMes)] (2) was synthesized from the Mn(III) complex [(TBP8Cz)Mn(III)] (1) and thermolysis of mesityl azide. An X-ray structure of 2 reveals a short Mn-N distance [1.595(4) A], consistent with the Mn-N triple bond expected for a manganese(V) imido species.

Hydrogen atom abstraction by a high-valent manganese(V)-oxo corrolazine.

High-valent metal-oxo complexes are postulated as key intermediates for a wide range of enzymatic and synthetic processes. To gain an understanding of these processes, the reactivity of an isolated, well-characterized Mn(V)-oxo complex, (TBP8Cz)MnVO (1), (TBP8Cz = octakis(para-tert-butylphenyl)corrolazinato(3-)) has been examined. This complex has been shown to oxidize a series of substituted phenols (4-X-2,6-t-Bu2C6H2OH, X = C(CH3)3 (3), H, Me, OMe, CN), resulting in the production of phenoxyl radicals and the MnIII complex [(TBP8Cz)MnIII] (2).

Synthesis, characterization, and physicochemical properties of manganese(III) and manganese(V)-oxo corrolazines.

The structural and physicochemical properties of the manganese-corrolazine (Cz) complexes (TBP8Cz)Mn(V)O (1) and (TBP8Cz)Mn(III) (2) (TBP = p-tert-butylphenyl) have been determined. Recrystallization of 2 from toluene/MeOH resulted in the crystal structure of (TBP8Cz)Mn(III)(CH3OH) (2 x MeOH). The packing diagram of 2 x MeOH reveals hydrogen bonds between MeOH axial ligands and meso N atoms of adjacent molecules.