The ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) salts
Salts of the ruthenocenylmethylium cation, 1+, can be synthesized from the reaction of ruthenocenylmethanol with either Brønsted or Lewis acids. The X-ray crystal structures of the tetrakis{3,5-bis(trifluoromethyl)phenyl}borate and trifluoromethanesulfonate salts of 1+ reveal that the methylium carb...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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2001
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| _version_ | 1797095836454223872 |
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| author | Barlow, S Cowley, A Green, J Brunker, T Hascall, T |
| author_facet | Barlow, S Cowley, A Green, J Brunker, T Hascall, T |
| author_sort | Barlow, S |
| collection | OXFORD |
| description | Salts of the ruthenocenylmethylium cation, 1+, can be synthesized from the reaction of ruthenocenylmethanol with either Brønsted or Lewis acids. The X-ray crystal structures of the tetrakis{3,5-bis(trifluoromethyl)phenyl}borate and trifluoromethanesulfonate salts of 1+ reveal that the methylium carbon is bound to the ruthenium with Ru-C bond lengths in the range 2.251(9)-2.40(1) Å and confirm the description of the cation structure as η5-cyclopentadienyl-η6-fulvene-ruthenium(II). The UV-vis spectrum of 1+ shows a d-d transition at an energy similar to those of ruthenocene and the η5-cyclopentadienyl-η6-benzeneruthenium(II) cation, but with increased absorptivity. Cyclic voltammetry indicates that 1+ is reduced at considerably less negative potential than its isomer, the η5-cyclopentadienyl-η6-benzene-ruthenium(II) cation. Chemical reduction with sodium amalgam in tetrahydrofuran leads to the formation of methylruthenocene, 1,2-bis(ruthenocenyl)ethane, and bis(ruthenocenylmethyl)ether. Reaction of 1+ with triphenylphosphine affords the (ruthenocenylmethyl)triphenylphosphonium cation; the crystal structure of the dichloromethane solvate of its tetrafluoroborate salt has been determined. Density functional calculations closely reproduce the crystallographically determined geometry of 1+ and allow rationalization of some characteristics of its structures, spectroscopy, and reactivity. The calculations suggest that the ferrocenylmethylium cation, 3+, has a geometry similar to 1+ with similar orbital structure, albeit with considerably more d-character to the occupied frontier orbitals. |
| first_indexed | 2024-03-07T04:33:39Z |
| format | Journal article |
| id | oxford-uuid:cf2d7fa9-47f9-49bb-bbbe-43417da1c889 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:33:39Z |
| publishDate | 2001 |
| record_format | dspace |
| spelling | oxford-uuid:cf2d7fa9-47f9-49bb-bbbe-43417da1c8892022-03-27T07:40:44ZThe ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) saltsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:cf2d7fa9-47f9-49bb-bbbe-43417da1c889EnglishSymplectic Elements at Oxford2001Barlow, SCowley, AGreen, JBrunker, THascall, TSalts of the ruthenocenylmethylium cation, 1+, can be synthesized from the reaction of ruthenocenylmethanol with either Brønsted or Lewis acids. The X-ray crystal structures of the tetrakis{3,5-bis(trifluoromethyl)phenyl}borate and trifluoromethanesulfonate salts of 1+ reveal that the methylium carbon is bound to the ruthenium with Ru-C bond lengths in the range 2.251(9)-2.40(1) Å and confirm the description of the cation structure as η5-cyclopentadienyl-η6-fulvene-ruthenium(II). The UV-vis spectrum of 1+ shows a d-d transition at an energy similar to those of ruthenocene and the η5-cyclopentadienyl-η6-benzeneruthenium(II) cation, but with increased absorptivity. Cyclic voltammetry indicates that 1+ is reduced at considerably less negative potential than its isomer, the η5-cyclopentadienyl-η6-benzene-ruthenium(II) cation. Chemical reduction with sodium amalgam in tetrahydrofuran leads to the formation of methylruthenocene, 1,2-bis(ruthenocenyl)ethane, and bis(ruthenocenylmethyl)ether. Reaction of 1+ with triphenylphosphine affords the (ruthenocenylmethyl)triphenylphosphonium cation; the crystal structure of the dichloromethane solvate of its tetrafluoroborate salt has been determined. Density functional calculations closely reproduce the crystallographically determined geometry of 1+ and allow rationalization of some characteristics of its structures, spectroscopy, and reactivity. The calculations suggest that the ferrocenylmethylium cation, 3+, has a geometry similar to 1+ with similar orbital structure, albeit with considerably more d-character to the occupied frontier orbitals. |
| spellingShingle | Barlow, S Cowley, A Green, J Brunker, T Hascall, T The ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) salts |
| title | The ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) salts |
| title_full | The ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) salts |
| title_fullStr | The ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) salts |
| title_full_unstemmed | The ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) salts |
| title_short | The ruthenocenylmethylium cation: Isolation and structures of eta(5)-cyclopentadienyl-eta(6)-fulvene-ruthenium(II) salts |
| title_sort | ruthenocenylmethylium cation isolation and structures of eta 5 cyclopentadienyl eta 6 fulvene ruthenium ii salts |
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