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

• Published in: Organometallics Vol. 35; no. 16; pp. 2683 - 2688
• Main Authors: Stalzer, Madelyn M, Telser, Joshua, Krzystek, Jurek, Motta, Alessandro, Delferro, Massimiliano, Marks, Tobin J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 22.08.2016
• Subjects: INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.6b00422

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.