Convenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexes
Carbene-induced rearrangement of 8,8-dibromobicyclo[5.1.0]octa-2,4-dienes and subsequent in situ deprotonation of the dihydropentalenes formed represents a straightforward and versatile solution route to pentalene ligands for use in organometallic chemistry. We report here the synthesis of 6-alkyl-s...
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| Format: | Journal article |
| Language: | English |
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2006
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| _version_ | 1797080093576658944 |
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| author | Jones, S Roussel, P Hascall, T O'Hare, D |
| author_facet | Jones, S Roussel, P Hascall, T O'Hare, D |
| author_sort | Jones, S |
| collection | OXFORD |
| description | Carbene-induced rearrangement of 8,8-dibromobicyclo[5.1.0]octa-2,4-dienes and subsequent in situ deprotonation of the dihydropentalenes formed represents a straightforward and versatile solution route to pentalene ligands for use in organometallic chemistry. We report here the synthesis of 6-alkyl-substituted 8,8-dibromobicyclo[5.1.0]octa-2,4-dienes and their rearrangement to give correspondingly substituted pentalene ligands. Generation of methyl-substituted dihydropentalenes from 8,8-dibromo-6-methylbicyclo[5.1.0]octa-2,4-diene followed by monodeprotonation with TlOEt gives methylhydropentalenyl salts, Tl(C 8H6Me), as a mixture of isomers. Formation of both 1-Me and 3-Me isomers of Re(C8H6Me)(CO)3 from these Tl species shows that monodeprotonation of the dihydropentalenes occurs at the unsubstituted ring. No evidence for the 2-Me isomer is observed, consistent with the rearrangement mechanism reported in the literature. Likewise, rearrangement of 8,8-dibromo-6-alkylbicyclo[5.1.0]octa-2,4-dienes (R = Me, Et, iPr) and subsequent double deprotonation with nBuLi in the presence of DME affords the pentalenyl salts Li2(C8H 5R)·xDME. X-ray crystallographic studies of the dinuclear Mn organometallics anti-[Mn(CO3]2(C8H 5R) synthesized from the Li salts confirm that these alkylated pentalene ligands are substituted at the 1-position exclusively. The crystal structure of a model hydropentalenyl complex, Re(C8H 7)(CO)3, is also reported. © 2006 American Chemical Society. |
| first_indexed | 2024-03-07T00:55:13Z |
| format | Journal article |
| id | oxford-uuid:87d5f70f-8d42-47d1-9c50-5bd881adbfbc |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T00:55:13Z |
| publishDate | 2006 |
| record_format | dspace |
| spelling | oxford-uuid:87d5f70f-8d42-47d1-9c50-5bd881adbfbc2022-03-26T22:13:07ZConvenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:87d5f70f-8d42-47d1-9c50-5bd881adbfbcEnglishSymplectic Elements at Oxford2006Jones, SRoussel, PHascall, TO'Hare, DCarbene-induced rearrangement of 8,8-dibromobicyclo[5.1.0]octa-2,4-dienes and subsequent in situ deprotonation of the dihydropentalenes formed represents a straightforward and versatile solution route to pentalene ligands for use in organometallic chemistry. We report here the synthesis of 6-alkyl-substituted 8,8-dibromobicyclo[5.1.0]octa-2,4-dienes and their rearrangement to give correspondingly substituted pentalene ligands. Generation of methyl-substituted dihydropentalenes from 8,8-dibromo-6-methylbicyclo[5.1.0]octa-2,4-diene followed by monodeprotonation with TlOEt gives methylhydropentalenyl salts, Tl(C 8H6Me), as a mixture of isomers. Formation of both 1-Me and 3-Me isomers of Re(C8H6Me)(CO)3 from these Tl species shows that monodeprotonation of the dihydropentalenes occurs at the unsubstituted ring. No evidence for the 2-Me isomer is observed, consistent with the rearrangement mechanism reported in the literature. Likewise, rearrangement of 8,8-dibromo-6-alkylbicyclo[5.1.0]octa-2,4-dienes (R = Me, Et, iPr) and subsequent double deprotonation with nBuLi in the presence of DME affords the pentalenyl salts Li2(C8H 5R)·xDME. X-ray crystallographic studies of the dinuclear Mn organometallics anti-[Mn(CO3]2(C8H 5R) synthesized from the Li salts confirm that these alkylated pentalene ligands are substituted at the 1-position exclusively. The crystal structure of a model hydropentalenyl complex, Re(C8H 7)(CO)3, is also reported. © 2006 American Chemical Society. |
| spellingShingle | Jones, S Roussel, P Hascall, T O'Hare, D Convenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexes |
| title | Convenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexes |
| title_full | Convenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexes |
| title_fullStr | Convenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexes |
| title_full_unstemmed | Convenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexes |
| title_short | Convenient solution route to alkylated pentalene ligands: New metal monoalkylpentalenyl complexes |
| title_sort | convenient solution route to alkylated pentalene ligands new metal monoalkylpentalenyl complexes |
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