[superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand
A series of asymmetrically carboxylate-bridged diiron(II) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe[subscript 2](PIM)(Ar[superscript 4F-Ph]CO[subscript 2])[subscript 2]] (10), [Fe[subscript 2](F[subscript 2]PIM)(Ar[superscript Tol]CO[subscript 2])[subscript 2]] (11), and [F...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2017
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| Online Access: | http://hdl.handle.net/1721.1/109585 https://orcid.org/0000-0002-8346-9570 https://orcid.org/0000-0002-2693-4982 |
| _version_ | 1826212189154836480 |
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| author | Minier, Mikael Antoine Lippard, Stephen J. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Minier, Mikael Antoine Lippard, Stephen J. |
| author_sort | Minier, Mikael Antoine |
| collection | MIT |
| description | A series of asymmetrically carboxylate-bridged diiron(II) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe[subscript 2](PIM)(Ar[superscript 4F-Ph]CO[subscript 2])[subscript 2]] (10), [Fe[subscript 2](F[subscript 2]PIM)(Ar[superscript Tol]CO[subscript 2])[subscript 2]] (11), and [Fe[subscript 2](F[subscript 2]PIM)(Ar[superscript 4F-Ph]CO[subscript 2])[superscript 2]] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT [superscript19]F NMR spectroscopy. These complexes are part of a rare family of syn-N diiron(II) complexes, [Fe[subscript 2](X[subscript 2]PIM)(RCO[subscript 2])[superscript 2]], that are structurally very similar to the active site of the hydroxylase enzyme component of reduced methane monooxygenase (MMOH[subscript red]). Solution characterization of these complexes demonstrates that they undergo intramolecular carboxylate rearrangements, or carboxylate shifts, a dynamic feature relevant to the reactivity of the diiron centers in bacterial multicomponent monooxygenases |
| first_indexed | 2024-09-23T15:17:46Z |
| format | Article |
| id | mit-1721.1/109585 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:17:46Z |
| publishDate | 2017 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/1095852022-09-29T14:01:09Z [superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand 19F NMR study of ligand dynamics in carboxylate-bridged diiron(II) complexes supported by a macrocyclic ligand Minier, Mikael Antoine Lippard, Stephen J. Massachusetts Institute of Technology. Department of Chemistry Minier, Mikael Antoine Lippard, Stephen J. A series of asymmetrically carboxylate-bridged diiron(II) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe[subscript 2](PIM)(Ar[superscript 4F-Ph]CO[subscript 2])[subscript 2]] (10), [Fe[subscript 2](F[subscript 2]PIM)(Ar[superscript Tol]CO[subscript 2])[subscript 2]] (11), and [Fe[subscript 2](F[subscript 2]PIM)(Ar[superscript 4F-Ph]CO[subscript 2])[superscript 2]] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT [superscript19]F NMR spectroscopy. These complexes are part of a rare family of syn-N diiron(II) complexes, [Fe[subscript 2](X[subscript 2]PIM)(RCO[subscript 2])[superscript 2]], that are structurally very similar to the active site of the hydroxylase enzyme component of reduced methane monooxygenase (MMOH[subscript red]). Solution characterization of these complexes demonstrates that they undergo intramolecular carboxylate rearrangements, or carboxylate shifts, a dynamic feature relevant to the reactivity of the diiron centers in bacterial multicomponent monooxygenases National Institute of General Medical Sciences (U.S.) (Grant GM 32114) National Science Foundation (U.S.). Graduate Research Fellowship Program (Grant 1122374) 2017-06-05T15:26:55Z 2017-06-05T15:26:55Z 2015-09 2015-06 Article http://purl.org/eprint/type/JournalArticle 1477-9226 1477-9234 http://hdl.handle.net/1721.1/109585 Minier, Mikael A., and Stephen J. Lippard. “[superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand.” Dalton Trans. 44.41 (2015): 18111–18121. https://orcid.org/0000-0002-8346-9570 https://orcid.org/0000-0002-2693-4982 en_US http://dx.doi.org/10.1039/c5dt02138c Dalton Transactions Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Royal Society of Chemistry PMC |
| spellingShingle | Minier, Mikael Antoine Lippard, Stephen J. [superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand |
| title | [superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand |
| title_full | [superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand |
| title_fullStr | [superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand |
| title_full_unstemmed | [superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand |
| title_short | [superscript 19]F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand |
| title_sort | superscript 19 f nmr study of ligand dynamics in carboxylate bridged diiron ii complexes supported by a macrocyclic ligand |
| url | http://hdl.handle.net/1721.1/109585 https://orcid.org/0000-0002-8346-9570 https://orcid.org/0000-0002-2693-4982 |
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