<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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MDPI AG
2024-10-01
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| author | Ananya Saju Matthew R. Crawley Samantha N. MacMillan Pierre Le Magueres Mark Del Campo David C. Lacy |
| author_facet | Ananya Saju Matthew R. Crawley Samantha N. MacMillan Pierre Le Magueres Mark Del Campo David C. Lacy |
| author_sort | Ananya Saju |
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| description | 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. |
| format | Article |
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| publishDate | 2024-10-01 |
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| spelling | doaj-art-d45e5cdcfd2d4d70909aa0fb5e5b787a2025-08-20T02:16:54ZengMDPI AGMolecules1420-30492024-10-012919467010.3390/molecules29194670<i>N</i>-Oxide Coordination to Mn(III) ChlorideAnanya Saju0Matthew R. Crawley1Samantha N. MacMillan2Pierre Le Magueres3Mark Del Campo4David C. Lacy5Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260, USADepartment of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260, USADepartment of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, USARigaku Americas, The Woodlands, TX 77381, USARigaku Americas, The Woodlands, TX 77381, USADepartment of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260, USAWe 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.https://www.mdpi.com/1420-3049/29/19/4670Mn(III)<i>N</i>-oxide ligandscoordination chemistryC–H chlorination |
| spellingShingle | Ananya Saju Matthew R. Crawley Samantha N. MacMillan Pierre Le Magueres Mark Del Campo David C. Lacy <i>N</i>-Oxide Coordination to Mn(III) Chloride Molecules Mn(III) <i>N</i>-oxide ligands coordination chemistry C–H chlorination |
| title | <i>N</i>-Oxide Coordination to Mn(III) Chloride |
| title_full | <i>N</i>-Oxide Coordination to Mn(III) Chloride |
| title_fullStr | <i>N</i>-Oxide Coordination to Mn(III) Chloride |
| title_full_unstemmed | <i>N</i>-Oxide Coordination to Mn(III) Chloride |
| title_short | <i>N</i>-Oxide Coordination to Mn(III) Chloride |
| title_sort | i n i oxide coordination to mn iii chloride |
| topic | Mn(III) <i>N</i>-oxide ligands coordination chemistry C–H chlorination |
| url | https://www.mdpi.com/1420-3049/29/19/4670 |
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