Taming a monomeric [Cu(η6 -C6 H6 )]+ complex with silylene

Chemical Science
Nasrina ParvinShabana Khan

Abstract

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.

References

Aug 19, 2007·Proceedings of the National Academy of Sciences of the United States of America·Vincent LavalloGuy Bertrand
Apr 17, 2010·Journal of the American Chemical Society·Erin R JohnsonWeitao Yang
Jul 14, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Silvia Díez-GonzálezSteven P Nolan
Sep 10, 2010·Journal of the American Chemical Society·Wenyuan WangMatthias Driess
Mar 25, 2011·Nature Chemistry·Jorge EcheverríaSantiago Alvarez
Feb 10, 2016·Chemical Communications : Chem Comm·Shabana KhanPattiyil Parameswaran
May 10, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Nasrina ParvinShabana Khan

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Citations

Oct 26, 2018·Chemical Communications : Chem Comm·Philipp Frisch, Shigeyoshi Inoue
Jun 10, 2020·Chemical Communications : Chem Comm·Nasrina ParvinShabana Khan
Nov 27, 2020·Chemistry : a European Journal·Steffen A FöhrenbacherUdo Radius
Jul 9, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Moushakhi Ghosh, Shabana Khan
Apr 27, 2019·Inorganic Chemistry·Alexander N PaeschDietmar Stalke
Jan 9, 2020·Inorganic Chemistry·Andrew W CookTrevor W Hayton
Aug 4, 2021·Chemistry : a European Journal·Sebastian PlanerMatthias Tamm

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Methods Mentioned

BETA
NMR
X-ray

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