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Issue 18, 2018
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Taming a monomeric [Cu(η6-C6H6)]+ complex with silylene

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Abstract

Previous theoretical and experimental endeavors suggested that [Cu(C6H6)]+ prefers the η12 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.

Graphical abstract: Taming a monomeric [Cu(η6-C6H6)]+ complex with silylene

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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., 2018,9, 4333-4337
  • Open access: Creative Commons BY license
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    Taming a monomeric [Cu(η6-C6H6)]+ complex with silylene

    N. Parvin, S. Pal, J. Echeverría, S. Alvarez and S. Khan, Chem. Sci., 2018, 9, 4333
    DOI: 10.1039/C8SC00459E

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