Electronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theory
He I and He II photoelectron (PE) spectra of [Fe(η-C2H4)2SiMe2] (1), [Fe(η-C5H3Me)2SiMe2] (2), [Fe(η-C5H4)(η-C5Me 4)SiMe2] (3), [Fe(η-C5Me4)2SiMe2] (4), [Fe(η-C5H4)2C2H4] (5), and [Fe-(η-C5H4)2S] (6) have been measured and assigned. The d bands of 1-5 show less structure than that of ferrocene, cons...
| Main Authors: | , , , , , , , , , , |
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| Format: | Journal article |
| Language: | English |
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1998
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| _version_ | 1797059545227329536 |
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| author | Barlow, S Drewitt, M Dijkstra, T Green, J O'Hare, D Whittingham, C Wynn, H Gates, D Manners, I Nelson, J Pudelski, J |
| author_facet | Barlow, S Drewitt, M Dijkstra, T Green, J O'Hare, D Whittingham, C Wynn, H Gates, D Manners, I Nelson, J Pudelski, J |
| author_sort | Barlow, S |
| collection | OXFORD |
| description | He I and He II photoelectron (PE) spectra of [Fe(η-C2H4)2SiMe2] (1), [Fe(η-C5H3Me)2SiMe2] (2), [Fe(η-C5H4)(η-C5Me 4)SiMe2] (3), [Fe(η-C5Me4)2SiMe2] (4), [Fe(η-C5H4)2C2H4] (5), and [Fe-(η-C5H4)2S] (6) have been measured and assigned. The d bands of 1-5 show less structure than that of ferrocene, consistent with a loss of degeneracy of the e2 orbitale on bending. Compound 6, which has the largest inter-ring angle of the series, shows two separate d bands. The trend in the first ionization energy closely parallels the variation in oxidation potential. Density functional calculations on 1, 5, and 6 give geometries in good agreement with the structures found from X-ray diffraction. Ionization energies calculated were also in excellent agreement with experiment. Good agreement was also found between the calculated d-d transitions and the position of the first spin-allowed band in the optical spectra of 1 and 6. Estimates of strain energy in bending ferrocene and octamethylferrocene were obtained, and octamethylferrocene was shown to be significantly more difficult to bend. Compounds 1 and 6 were both shown to have a low-lying empty orbital, partially located on the ipso carbon, which is a possible site for nucleophilic attack in the polymerization process undergone by these compounds. |
| first_indexed | 2024-03-06T20:05:49Z |
| format | Journal article |
| id | oxford-uuid:28df10ea-6708-4e70-8c64-a41414c0138b |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T20:05:49Z |
| publishDate | 1998 |
| record_format | dspace |
| spelling | oxford-uuid:28df10ea-6708-4e70-8c64-a41414c0138b2022-03-26T12:15:35ZElectronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theoryJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:28df10ea-6708-4e70-8c64-a41414c0138bEnglishSymplectic Elements at Oxford1998Barlow, SDrewitt, MDijkstra, TGreen, JO'Hare, DWhittingham, CWynn, HGates, DManners, INelson, JPudelski, JHe I and He II photoelectron (PE) spectra of [Fe(η-C2H4)2SiMe2] (1), [Fe(η-C5H3Me)2SiMe2] (2), [Fe(η-C5H4)(η-C5Me 4)SiMe2] (3), [Fe(η-C5Me4)2SiMe2] (4), [Fe(η-C5H4)2C2H4] (5), and [Fe-(η-C5H4)2S] (6) have been measured and assigned. The d bands of 1-5 show less structure than that of ferrocene, consistent with a loss of degeneracy of the e2 orbitale on bending. Compound 6, which has the largest inter-ring angle of the series, shows two separate d bands. The trend in the first ionization energy closely parallels the variation in oxidation potential. Density functional calculations on 1, 5, and 6 give geometries in good agreement with the structures found from X-ray diffraction. Ionization energies calculated were also in excellent agreement with experiment. Good agreement was also found between the calculated d-d transitions and the position of the first spin-allowed band in the optical spectra of 1 and 6. Estimates of strain energy in bending ferrocene and octamethylferrocene were obtained, and octamethylferrocene was shown to be significantly more difficult to bend. Compounds 1 and 6 were both shown to have a low-lying empty orbital, partially located on the ipso carbon, which is a possible site for nucleophilic attack in the polymerization process undergone by these compounds. |
| spellingShingle | Barlow, S Drewitt, M Dijkstra, T Green, J O'Hare, D Whittingham, C Wynn, H Gates, D Manners, I Nelson, J Pudelski, J Electronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theory |
| title | Electronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theory |
| title_full | Electronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theory |
| title_fullStr | Electronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theory |
| title_full_unstemmed | Electronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theory |
| title_short | Electronic structure of strained silicon- and sulfur-bridged [1]ferrocenophanes and an analogous dicarbon-bridged [2]ferrocenophane: An investigation by photoelectron spectroscopy and density-functional theory |
| title_sort | electronic structure of strained silicon and sulfur bridged 1 ferrocenophanes and an analogous dicarbon bridged 2 ferrocenophane an investigation by photoelectron spectroscopy and density functional theory |
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