<i>N</i>-Oxide Coordination to Mn(III) Chloride

<i>N</i>-Oxide Coordination to Mn(III) Chloride

We report on the synthesis and characterization of Mn(III) chloride (Mn<sup>III</sup>Cl<sub>3</sub>) complexes coordinated with <i>N</i>-oxide ylide ligands, namely trimethyl-<i>N</i>-oxide (Me<sub>3</sub>NO) and pyridine-<i>N</i&g...

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Bibliographic Details
Main Authors:	Ananya Saju, Matthew R. Crawley, Samantha N. MacMillan, Pierre Le Magueres, Mark Del Campo, David C. Lacy
Format:	Article
Language:	English
Published:	MDPI AG 2024-10-01
Series:	Molecules
Subjects:	Mn(III) <i>N</i>-oxide ligands coordination chemistry C–H chlorination
Online Access:	https://www.mdpi.com/1420-3049/29/19/4670
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Summary:	We report on the synthesis and characterization of Mn(III) chloride (Mn<sup>III</sup>Cl<sub>3</sub>) complexes coordinated with <i>N</i>-oxide ylide ligands, namely trimethyl-<i>N</i>-oxide (Me<sub>3</sub>NO) and pyridine-<i>N</i>-oxide (PyNO). The compounds are reactive and, while isolable in the solid-state at room temperature, readily decompose into Mn(II). For example, “[Mn<sup>III</sup>Cl<sub>3</sub>(ONMe<sub>3</sub>)<sub>n</sub>]” decomposes into the 2D polymeric network compound complex salt [Mn<sup>II</sup>(µ-Cl)<sub>3</sub>Mn<sup>II</sup>(µ-ONMe<sub>3</sub>)]<sub>n</sub>[Mn<sup>II</sup>(µ-Cl)<sub>3</sub>]<sub>n</sub>·(Me<sub>3</sub>NO·HCl)<sub>3n</sub> (<b>4</b>). The reaction of Mn<sup>III</sup>Cl<sub>3</sub> 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 (<b>8</b>). In contrast to <i>N</i>-oxide coordination to Mn(III), the reaction between [Mn<sup>III</sup>Cl<sub>3</sub>(OPPh<sub>3</sub>)<sub>2</sub>] and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) resulted in electron transfer-forming <i>d</i><sup>5</sup> manganate of the [TEMPO] cation instead of TEMPO–Mn(III) adducts. The reactivity affected by <i>N</i>-oxide coordination is discussed through comparisons with other L–Mn<sup>III</sup>Cl<sub>3</sub> complexes within the context of reduction potential.
ISSN:	1420-3049