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. This high-valent species is remarkably inert to one- and two-electron reductive processes such as NR group transfer to alkenes or H-atom abstraction from O-H bonds. Electrochemical studies support this lack of reactivity. In contrast, oxidation of 2 is easily accomplished by treatment with [(4-BrC6H4)3N]*+SbCl6, giving a pi-radical-cation complex.
Lansky
David E
DE
Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA.
Kosack
Joseph R
JR
Narducci Sarjeant
Amy A
AA
Goldberg
David P
DP
D007094:Imides / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D017895:Manganese Compounds / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D011199:Potentiometry; D013053:Spectrophotometry
D007094:Imides; D017895:Manganese Compounds; D008665:Metalloporphyrins