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Issue 18, 2018

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

Supplementary files

Article information


Submitted
29 Jan 2018
Accepted
12 Apr 2018
First published
13 Apr 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 4333-4337
Article type
Edge Article

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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