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

Evans, Kieren J. ORCID:, 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: 10 Nov 2022 10:02

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