Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species
A new, DMF-coordinated, preorganized diiron compound [Fe[subscript 2](N-Et-HPTB)(DMF)[subscript 4]](BF[subscript 4])[subscript 3] (1) was synthesized, avoiding the formation of [Fe(N-Et-HPTB)](BF4)2 (10) and [Fe2(N-Et-HPTB)(μ-MeCONH)](BF[subscript 4])[subscript 2] (11), where N-Et-HPTB is the anion...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2015
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| Online Access: | http://hdl.handle.net/1721.1/95498 https://orcid.org/0000-0002-2693-4982 https://orcid.org/0000-0002-1577-2420 |
| _version_ | 1826206621897850880 |
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| author | Majumdar, Amit Apfel, Ulf-Peter Jiang, Yunbo Moenne-Loccoz, Pierre Lippard, Stephen J. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Majumdar, Amit Apfel, Ulf-Peter Jiang, Yunbo Moenne-Loccoz, Pierre Lippard, Stephen J. |
| author_sort | Majumdar, Amit |
| collection | MIT |
| description | A new, DMF-coordinated, preorganized diiron compound [Fe[subscript 2](N-Et-HPTB)(DMF)[subscript 4]](BF[subscript 4])[subscript 3] (1) was synthesized, avoiding the formation of [Fe(N-Et-HPTB)](BF4)2 (10) and [Fe2(N-Et-HPTB)(μ-MeCONH)](BF[subscript 4])[subscript 2] (11), where N-Et-HPTB is the anion of N,N,N′,N′-tetrakis[2-(1-ethylbenzimidazolyl)]-2-hydroxy-1,3-diaminopropane. Compound 1 is a versatile reactant from which nine new compounds have been generated. Transformations include solvent exchange to yield [Fe[subscript 2](N-Et-HPTB)(MeCN)[subscript 4]](BF[subscript 4])[subscript 3] (2), substitution to afford [Fe[subscript 2](N-Et-HPTB)(μ-RCOO)](BF[subscript 4])[subscript 2] (3, R = Ph; 4, RCOO = 4-methyl-2,6-diphenyl benzoate]), one-electron oxidation by (Cp[subscript 2]Fe)(BF[subscript 4]) to yield a Robin–Day class II mixed-valent diiron(II,III) compound, [Fe[subscript 2](N-Et-HPTB)(μ-PhCOO)(DMF)[subscript 2]](BF[subscript 4])[subscript 3] (5), two-electron oxidation with tris(4-bromophenyl)aminium hexachloroantimonate to generate [Fe[subscript 2](N-Et-HPTB)Cl[subscript 3](DMF)](BF[subscript 4])[subscript 2] (6), reaction with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl to form [Fe[subscript 5](N-Et-HPTB)[subscript 2](μ-OH)[subscript 4](μ-O)(DMF)[subscript 2]](BF[subscript 4])[subscript 4] (7), and reaction with dioxygen to yield an unstable peroxo compound that decomposes at room temperature to generate [Fe[subscript 4](N-Et-HPTB)2(μ-O)[subscript 3](H[subscript 2]O)[subscript 2]](BF[subscript 4])·8DMF (8) and [Fe[subscript 4](N-Et-HPTB)[subscript 2](μ-O)[subscript 4]](BF[subscript 4])[subscript 2] (9). Compound 5 loses its bridging benzoate ligand upon further oxidation to form [Fe[subscript 2](N-Et-HPTB)(OH)[subscript 2](DMF)[subscript 2]](BF[subscript 4])[subscript 3] (12). Reaction of the diiron(II,III) compound 5 with dioxygen was studied in detail by spectroscopic methods. All compounds (1–12) were characterized by single-crystal X-ray structure determinations. Selected compounds and reaction intermediates were further examined by a combination of elemental analysis, electronic absorption spectroscopy, Mössbauer spectroscopy, EPR spectroscopy, resonance Raman spectroscopy, and cyclic voltammetry. |
| first_indexed | 2024-09-23T13:35:30Z |
| format | Article |
| id | mit-1721.1/95498 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:35:30Z |
| publishDate | 2015 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/954982022-09-28T14:52:38Z Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species Majumdar, Amit Apfel, Ulf-Peter Jiang, Yunbo Moenne-Loccoz, Pierre Lippard, Stephen J. Massachusetts Institute of Technology. Department of Chemistry Majumdar, Amit Apfel, Ulf-Peter Lippard, Stephen J. A new, DMF-coordinated, preorganized diiron compound [Fe[subscript 2](N-Et-HPTB)(DMF)[subscript 4]](BF[subscript 4])[subscript 3] (1) was synthesized, avoiding the formation of [Fe(N-Et-HPTB)](BF4)2 (10) and [Fe2(N-Et-HPTB)(μ-MeCONH)](BF[subscript 4])[subscript 2] (11), where N-Et-HPTB is the anion of N,N,N′,N′-tetrakis[2-(1-ethylbenzimidazolyl)]-2-hydroxy-1,3-diaminopropane. Compound 1 is a versatile reactant from which nine new compounds have been generated. Transformations include solvent exchange to yield [Fe[subscript 2](N-Et-HPTB)(MeCN)[subscript 4]](BF[subscript 4])[subscript 3] (2), substitution to afford [Fe[subscript 2](N-Et-HPTB)(μ-RCOO)](BF[subscript 4])[subscript 2] (3, R = Ph; 4, RCOO = 4-methyl-2,6-diphenyl benzoate]), one-electron oxidation by (Cp[subscript 2]Fe)(BF[subscript 4]) to yield a Robin–Day class II mixed-valent diiron(II,III) compound, [Fe[subscript 2](N-Et-HPTB)(μ-PhCOO)(DMF)[subscript 2]](BF[subscript 4])[subscript 3] (5), two-electron oxidation with tris(4-bromophenyl)aminium hexachloroantimonate to generate [Fe[subscript 2](N-Et-HPTB)Cl[subscript 3](DMF)](BF[subscript 4])[subscript 2] (6), reaction with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl to form [Fe[subscript 5](N-Et-HPTB)[subscript 2](μ-OH)[subscript 4](μ-O)(DMF)[subscript 2]](BF[subscript 4])[subscript 4] (7), and reaction with dioxygen to yield an unstable peroxo compound that decomposes at room temperature to generate [Fe[subscript 4](N-Et-HPTB)2(μ-O)[subscript 3](H[subscript 2]O)[subscript 2]](BF[subscript 4])·8DMF (8) and [Fe[subscript 4](N-Et-HPTB)[subscript 2](μ-O)[subscript 4]](BF[subscript 4])[subscript 2] (9). Compound 5 loses its bridging benzoate ligand upon further oxidation to form [Fe[subscript 2](N-Et-HPTB)(OH)[subscript 2](DMF)[subscript 2]](BF[subscript 4])[subscript 3] (12). Reaction of the diiron(II,III) compound 5 with dioxygen was studied in detail by spectroscopic methods. All compounds (1–12) were characterized by single-crystal X-ray structure determinations. Selected compounds and reaction intermediates were further examined by a combination of elemental analysis, electronic absorption spectroscopy, Mössbauer spectroscopy, EPR spectroscopy, resonance Raman spectroscopy, and cyclic voltammetry. National Institute of General Medical Sciences (U.S.) (Grant GM032134) Alexander von Humboldt-Stiftung (Postdoctoral Fellowship) 2015-02-24T20:55:47Z 2015-02-24T20:55:47Z 2013-12 2013-07 Article http://purl.org/eprint/type/JournalArticle 0020-1669 1520-510X http://hdl.handle.net/1721.1/95498 Majumdar, Amit, Ulf-Peter Apfel, Yunbo Jiang, Pierre Moënne-Loccoz, and Stephen J. Lippard. “ Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species .” Inorg. Chem. 53, no. 1 (January 6, 2014): 167–181. https://orcid.org/0000-0002-2693-4982 https://orcid.org/0000-0002-1577-2420 en_US http://dx.doi.org/10.1021/ic4019585 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) PMC |
| spellingShingle | Majumdar, Amit Apfel, Ulf-Peter Jiang, Yunbo Moenne-Loccoz, Pierre Lippard, Stephen J. Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species |
| title | Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species |
| title_full | Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species |
| title_fullStr | Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species |
| title_full_unstemmed | Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species |
| title_short | Versatile Reactivity of a Solvent-Coordinated Diiron(II) Compound: Synthesis and Dioxygen Reactivity of a Mixed-Valent Fe [superscript II] Fe [superscript III] Species |
| title_sort | versatile reactivity of a solvent coordinated diiron ii compound synthesis and dioxygen reactivity of a mixed valent fe superscript ii fe superscript iii species |
| url | http://hdl.handle.net/1721.1/95498 https://orcid.org/0000-0002-2693-4982 https://orcid.org/0000-0002-1577-2420 |
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