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Taming Monomeric [Cu(η6-C6H6)]+ Complex with Silylene

Abstract

Previous theoretical and experimental endeavors suggested that [Cu(C6H6)]+ prefers η1/η2 mode over 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 copper atom is bound to the benzene ring in 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 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 η6 mode in 2 while NHC copper cation displays η3 bonding mode in 5. DFT calculations are carried out to understand how the use of silylene led to η6 binding mode and why IPr afforded η2 binding mode.

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Publication details

The article was received on 29 Jan 2018, accepted on 12 Apr 2018 and first published on 13 Apr 2018


Article type: Edge Article
DOI: 10.1039/C8SC00459E
Citation: Chem. Sci., 2018, Accepted Manuscript
  • Open access: Creative Commons BY license
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    Taming Monomeric [Cu(η6-C6H6)]+ Complex with Silylene

    N. Parvin, S. Pal, J. Echeverría, S. Álvarez and S. Khan, Chem. Sci., 2018, Accepted Manuscript , DOI: 10.1039/C8SC00459E

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