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Lithium complexes with bridging and terminal NHC ligands: the decisive influence of an anionic tether

Evans, Kieren J., Campbell, Cameron L., Haddow, Mairi F., Luz, Christian, Morton, Paul A. and Mansell, Stephen M. 2019. Lithium complexes with bridging and terminal NHC ligands: the decisive influence of an anionic tether. European Journal of Inorganic Chemistry 2019 (46) , pp. 4894-4901. 10.1002/ejic.201901003

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Deprotonation of the fluorenyl-tethered imidazolinium salt [9-(C13H9)C2H4N(CH)C2H4N(2,4,6-Me3C6H2)][BF4] gave a spirocyclic compound that reacted with a synergic mixture of LiPh/LiN(SiMe3)2 or LinBu/LiN(SiMe3)2 to give a dilithium complex incorporating a bridging N(SiMe3)2 ligand. In contrast, deprotonation of the imidazolium salt [9-(C13H9)C2H4N(CH)C2H2N(Me)][Br] instead yielded the free NHC, which reacted with nBuLi to form a dimeric, NHC-bridged dilithium complex. Addition of LiN(SiMe3)2 led to coordination and the formation of a dilithium complex with a bridging N(SiMe3)2 ligand, which was characterised in the solid state as a 1D coordination polymer. The reaction of 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr) with lithium indenide and lithium fluorenide gave soluble species with terminal binding of the NHC to the lithium cation and η5 coordination of indenyl or fluorenyl. A symmetrical bridging mode for an NHC donor was therefore observed only if a tethered fluorenyl anion was present with no additional amide ligand.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: Wiley-VCH Verlag
ISSN: 1434-1948
Date of First Compliant Deposit: 15 November 2021
Date of Acceptance: 13 November 2019
Last Modified: 23 Nov 2021 19:10

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