-Oxide Coordination to Mn(III) Chloride.

We report on the synthesis and characterization of Mn(III) chloride (MnCl) complexes coordinated with -oxide ylide ligands, namely trimethyl--oxide (MeNO) and pyridine--oxide (PyNO). The compounds are reactive and, while isolable in the solid-state at room temperature, readily decompose into Mn(II). For example, "[MnCl(ONMe)]" decomposes into the 2D polymeric network compound complex salt [Mn(µ-Cl)Mn(µ-ONMe)][Mn(µ-Cl)]·(MeNO·HCl) (). The reaction of MnCl with PyNO forms varied Mn(III) compounds with PyNO coordination and these react with hexamethylbenzene (HMB) to form the chlorinated organic product 1-cloromethyl-2,3,4,5,6-pentamethylbenzene (). In contrast to -oxide coordination to Mn(III), the reaction between [MnCl(OPPh)] and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) resulted in electron transfer-forming manganate of the [TEMPO] cation instead of TEMPO-Mn(III) adducts. The reactivity affected by -oxide coordination is discussed through comparisons with other L-MnCl complexes within the context of reduction potential.