Taming a monomeric [Cu(η6-C6H6)]+ complex with silylene† †Electronic supplementary information (ESI) available: Experimental details of 2, 3, 5 and 6, their single crystal X-ray data, and details of theoretical calculations. CCDC 1540046, 1540047, 1547791, and 1547792. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc00459e ‡ ‡Dedicated to Prof. Krishna N. Ganesh on the occasion of his 65th birthday
| Autor: | Parvin, Nasrina, Pal, Shiv, Echeverría, Jorge, Alvarez, Santiago, Khan, Shabana |
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| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: | |
| Zdroj: | Chemical Science |
| ISSN: | 2041-6539 2041-6520 |
| Popis: | Realization of a hitherto elusive unsupported η6 binding mode of benzene to a copper(i) cation employing silylene as a ligand. The back-donation from Cu to Si(ii) diminishes the repulsion between d-electrons and the benzene ring and enforces the η6 binding mode. Previous theoretical and experimental endeavors suggested that [Cu(C6H6)]+ prefers the η1/η2 mode over the η6 mode due to the augmented repulsion between the benzene ring and metal d-electrons. Nevertheless, the use of silylene as a neutral ligand has led to the isolation of the first monomeric copper cation, [{PhC(NtBu)2SiN(SiMe3)2}Cu(η6-C6H6)]+[SbF6]– (3), where a copper atom is bound to the benzene ring in an unsupported η6 fashion. However, the use of IPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) in place of silylene results in the formation of [IPr·Cu(η2-C6H6)]+[SbF6]– (6), where the copper atom is bound to the benzene ring in the η2 mode. The discrepancy in hapticities is also reflected when hexamethylbenzene is employed as the arene ring. The silylene supported copper cation continues to bind in the η6 mode in 2 while the NHC copper cation displays an η3 bonding mode in 5. DFT calculations are carried out to understand how the use of silylene led to the η6 binding mode and why IPr afforded the η2 binding mode. |
| Databáze: | OpenAIRE |
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