A Neutrally Charged Trimethylmanganese(III) Complex: Synthesis, Characterization, and Disproportionation Chemistry

The synthesis and properties of an unusual, neutrally charged and volatile N,N,N′,N′-tetramethylethylenediamine trimethyl manganese(III) complex, (TMEDA)MnMe₃, are described, along with its facile disproportionation to the corresponding Mn(II) and Mn(IV) complexes. Characterization by single-crystal XRD, UV-vis spectroscopy, high-frequency and -field EPR (HFEPR), magnetic susceptibility, and density functional theory (DFT) computations indicate that the (TMEDA)MnMe₃ electronic structure can be described as largely square pyramidal Mn(III) centered. The paucity of manganese(III) polyalkyls and the simplicity and reactivity of this compound implicate it as a potentially useful synthetic building block.