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Extending motifs in lithiocuprate chemistry: unexpected structural diversity in thiocyanate complexes

Abstract : The new area of lithio(thiocyanato)cuprates has been developed. Using inexpensive, stable and safe CuSCN for their preparation, these complexes revealed Lipshutz-type dimeric motifs with solvent-dependent point group identities; planar, boat-shaped and chair shaped conformers are seen in the solid state. In solution, both Lipshutz-type and Gilman structures are clearly seen. Since the advent in 2007 of directed ortho cupration, effort has gone into understanding the structure-reactivity effects of amide ligand variation in and alkali metal salt abstraction from Lipshutz-type cuprates such as (TMP)2Cu(CN)Li2(THF) (TMP = 2,2,6,6-tetramethylpiperidide). The replacement of CN(-) with SCN(-) is investigated presently as a means of improving the safety of lithium cuprates. The synthesis and solid state structural characterization of reference cuprate (TMP)2Cu(CN)Li2(THP) (THP = tetrahydropyran) precedes that of the thiocyanate series (TMP)2Cu(SCN)Li2(L) (L = OEt2, THF , THP ). For each of , preformed TMPLi was combined with CuSCN (2 : 1) in the presence of sub-stoichiometric Lewis base (0.5 eq. wrt Li). The avoidance of Lewis basic solvents incurs formation of the unsolvated Gilman cuprate (TMP)2CuLi , whilst multidimensional NMR spectroscopy has evidenced the abstraction of LiSCN from in hydrocarbon solution and the in situ formation of Gilman reagents. The synthetic utility of is established in the selective deprotometalation of chloropyridine substrates, including effecting transition metal-free homocoupling in 51-69% yield
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Submitted on : Thursday, November 19, 2015 - 3:47:19 PM
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Andrew J. Peel, Madani Hedidi, Ghenia Bentabed-Ababsa, Thierry Roisnel, Florence Mongin, et al.. Extending motifs in lithiocuprate chemistry: unexpected structural diversity in thiocyanate complexes. Dalton Transactions, Royal Society of Chemistry, 2016, 45 (14), pp.6094-6104. ⟨10.1039/c5dt03882k⟩. ⟨hal-01231163⟩



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