Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1
Partial substitution of Zn[superscript II] by Mn[superscript II] in Zn[subscript 5](OAc)[subscript 4](5,5′-bibenzo[d][1,2,3]triazole)[subscript 3] (CFA-1) results in a Mn[superscript II] species supported by three nitrogen ligands and a charge-balancing anion, a structure reminiscent of those found...
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/126240 |
| _version_ | 1826210113130594304 |
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| author | Stubbs, Amanda Walcott Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Stubbs, Amanda Walcott Dinca, Mircea |
| author_sort | Stubbs, Amanda Walcott |
| collection | MIT |
| description | Partial substitution of Zn[superscript II] by Mn[superscript II] in Zn[subscript 5](OAc)[subscript 4](5,5′-bibenzo[d][1,2,3]triazole)[subscript 3] (CFA-1) results in a Mn[superscript II] species supported by three nitrogen ligands and a charge-balancing anion, a structure reminiscent of those found in molecular "scorpionate" complexes. Unlike molecular manganese(II) scorpionates, Mn-CFA-1 is capable of catalytically activating oxygen from air to oxidize C-H bonds up to 87 kcal/mol in strength. A series of in situ spectroscopic studies, including diffuse-reflectance UV-vis, diffuse-reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy, reveal that catalysis likely proceeds through a manganese(III) hydroperoxo that is only accessed in the presence of a hydrogen-atom donor. These results demonstrate that the site isolation provided in metal-organic frameworks enables the generation and utilization of highly reactive species for catalysis that are inaccessible in molecular systems. |
| first_indexed | 2024-09-23T14:43:37Z |
| format | Article |
| id | mit-1721.1/126240 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T14:43:37Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1262402022-10-01T22:10:03Z Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1 Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in Mn[superscript II]-exchanged CFA-1 Stubbs, Amanda Walcott Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry Partial substitution of Zn[superscript II] by Mn[superscript II] in Zn[subscript 5](OAc)[subscript 4](5,5′-bibenzo[d][1,2,3]triazole)[subscript 3] (CFA-1) results in a Mn[superscript II] species supported by three nitrogen ligands and a charge-balancing anion, a structure reminiscent of those found in molecular "scorpionate" complexes. Unlike molecular manganese(II) scorpionates, Mn-CFA-1 is capable of catalytically activating oxygen from air to oxidize C-H bonds up to 87 kcal/mol in strength. A series of in situ spectroscopic studies, including diffuse-reflectance UV-vis, diffuse-reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy, reveal that catalysis likely proceeds through a manganese(III) hydroperoxo that is only accessed in the presence of a hydrogen-atom donor. These results demonstrate that the site isolation provided in metal-organic frameworks enables the generation and utilization of highly reactive species for catalysis that are inaccessible in molecular systems. National Science Foundation (Award DMR1452612) National Science Foundation (Grant 1122374) 2020-07-17T18:48:20Z 2020-07-17T18:48:20Z 2019-09 2019-07 2019-12-17T15:38:54Z Article http://purl.org/eprint/type/JournalArticle 1520-510X https://hdl.handle.net/1721.1/126240 Stubbs, Amanda W., and Mircea Dincă. "Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1." Inorganic Chemistry 58, 19 (Sept. 2019): 13221-28 doi 10.1021/acs.inorgchem.9b02068 ©2019 Author(s) en 10.1021/acs.inorgchem.9b02068 Inorganic Chemistry Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) MIT web domain |
| spellingShingle | Stubbs, Amanda Walcott Dinca, Mircea Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1 |
| title | Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1 |
| title_full | Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1 |
| title_fullStr | Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1 |
| title_full_unstemmed | Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1 |
| title_short | Selective oxidation of C-H bonds through a manganese(III) hydroperoxo in MnII-exchanged CFA-1 |
| title_sort | selective oxidation of c h bonds through a manganese iii hydroperoxo in mnii exchanged cfa 1 |
| url | https://hdl.handle.net/1721.1/126240 |
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