Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters
The coordination chemistry of nitrogenous ligands at high-spin iron is investigated through the synthesis and characterization of a terminal imido complex of a cuboidal tetra(μ3-sulfido)tetrairon (Fe4S4) cluster. Structural, spectroscopic, and computational studies establish a dynamic interplay betw...
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| Format: | Thesis |
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Massachusetts Institute of Technology
2022
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| Online Access: | https://hdl.handle.net/1721.1/145013 https://orcid.org/0000-0001-9249-8894 |
| _version_ | 1826207810232254464 |
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| author | Sridharan, Arun |
| author2 | Suess, Daniel L.M. |
| author_facet | Suess, Daniel L.M. Sridharan, Arun |
| author_sort | Sridharan, Arun |
| collection | MIT |
| description | The coordination chemistry of nitrogenous ligands at high-spin iron is investigated through the synthesis and characterization of a terminal imido complex of a cuboidal tetra(μ3-sulfido)tetrairon (Fe4S4) cluster. Structural, spectroscopic, and computational studies establish a dynamic interplay between Fe–N, Fe–S, and Fe–Fe interactions, tuned by the Fe centers’ locally high-spin electron configurations and the pseudo-C3v symmetry of the imido-bound metal site. Reaction with 1,4-cyclohexadiene affords clean conversion to the corresponding [Fe4S4] anilido complex, which was characterized in two oxidation states. Oxidation and reduction of the [Fe4S4] terminal imido complex affords a four-membered redox series spanning the 1−/0/1+/2+ charge states. A combined spectroscopic and theoretical analysis of this redox series using variable-temperature 1H nuclear magnetic resonance spectroscopy reveals that oxidation events are primarily centered at the imido fragment, which takes on an iminyl ([NAr]•−) or triplet nitrene ([NAr]2•) configuration depending on the charge state of the molecule. Two-electron oxidation of [Fe4S4]+ anilido complexes results in formal aminyl radical reductive elimination, generating aniline, hydrazine, and/or azoarene as byproducts along with the corresponding [Fe4S4]2+ solvento adduct. Addition of 1,2-diarylhydrazine to the [Fe4S4]+ solvento adduct results in N–N binuclear oxidative addition to afford the [Fe4S4]2+ anilido complex, which upon further reaction with 1,2-diarylhydrazines catalyzes their disproportionation to aniline and azoarene. The development of new synthetic platforms for investigating the reaction chemistry of iron–sulfur clusters is described: [MFe3S4] cluster cubanes are prepared varying the identity of the heterometal (Mo or V) and the steric profile of its supporting ligand for application in studies of dinitrogen binding and functionalization. The discovery of a new tridentate ligand topology for cuboidal [Fe4S4] clusters incorporating 1,1′-biphenyl-3,3′-diyl linkers is reported, along with strategies for metalating its tris(phosphine) derivative. |
| first_indexed | 2024-09-23T13:55:18Z |
| format | Thesis |
| id | mit-1721.1/145013 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T13:55:18Z |
| publishDate | 2022 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/1450132022-08-30T03:25:28Z Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters Sridharan, Arun Suess, Daniel L.M. Massachusetts Institute of Technology. Department of Chemistry The coordination chemistry of nitrogenous ligands at high-spin iron is investigated through the synthesis and characterization of a terminal imido complex of a cuboidal tetra(μ3-sulfido)tetrairon (Fe4S4) cluster. Structural, spectroscopic, and computational studies establish a dynamic interplay between Fe–N, Fe–S, and Fe–Fe interactions, tuned by the Fe centers’ locally high-spin electron configurations and the pseudo-C3v symmetry of the imido-bound metal site. Reaction with 1,4-cyclohexadiene affords clean conversion to the corresponding [Fe4S4] anilido complex, which was characterized in two oxidation states. Oxidation and reduction of the [Fe4S4] terminal imido complex affords a four-membered redox series spanning the 1−/0/1+/2+ charge states. A combined spectroscopic and theoretical analysis of this redox series using variable-temperature 1H nuclear magnetic resonance spectroscopy reveals that oxidation events are primarily centered at the imido fragment, which takes on an iminyl ([NAr]•−) or triplet nitrene ([NAr]2•) configuration depending on the charge state of the molecule. Two-electron oxidation of [Fe4S4]+ anilido complexes results in formal aminyl radical reductive elimination, generating aniline, hydrazine, and/or azoarene as byproducts along with the corresponding [Fe4S4]2+ solvento adduct. Addition of 1,2-diarylhydrazine to the [Fe4S4]+ solvento adduct results in N–N binuclear oxidative addition to afford the [Fe4S4]2+ anilido complex, which upon further reaction with 1,2-diarylhydrazines catalyzes their disproportionation to aniline and azoarene. The development of new synthetic platforms for investigating the reaction chemistry of iron–sulfur clusters is described: [MFe3S4] cluster cubanes are prepared varying the identity of the heterometal (Mo or V) and the steric profile of its supporting ligand for application in studies of dinitrogen binding and functionalization. The discovery of a new tridentate ligand topology for cuboidal [Fe4S4] clusters incorporating 1,1′-biphenyl-3,3′-diyl linkers is reported, along with strategies for metalating its tris(phosphine) derivative. Ph.D. 2022-08-29T16:27:15Z 2022-08-29T16:27:15Z 2022-05 2022-06-08T13:05:34.787Z Thesis https://hdl.handle.net/1721.1/145013 https://orcid.org/0000-0001-9249-8894 In Copyright - Educational Use Permitted Copyright MIT http://rightsstatements.org/page/InC-EDU/1.0/ application/pdf Massachusetts Institute of Technology |
| spellingShingle | Sridharan, Arun Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters |
| title | Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters |
| title_full | Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters |
| title_fullStr | Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters |
| title_full_unstemmed | Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters |
| title_short | Investigations of Iron–Nitrogen Bonding at Synthetic Iron–Sulfur Clusters |
| title_sort | investigations of iron nitrogen bonding at synthetic iron sulfur clusters |
| url | https://hdl.handle.net/1721.1/145013 https://orcid.org/0000-0001-9249-8894 |
| work_keys_str_mv | AT sridharanarun investigationsofironnitrogenbondingatsyntheticironsulfurclusters |