The changing structural chemistry of lithium anilide on solvation by pyridine, 4-methylpyridine or 4-tert-butylpyridine

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Clegg, W and Horsburgh, L and Liddle, S T and Mackenzie, F M and Mulvey, Robert and Robertson, A (2000) The changing structural chemistry of lithium anilide on solvation by pyridine, 4-methylpyridine or 4-tert-butylpyridine. Journal of the Chemical Society, Dalton Transactions, 7. pp. 1225-1231. ISSN 0300-9246 (https://doi.org/10.1039/B000576M)

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Abstract

A family of crystalline lithium anilide solvates, [{PhN(H)Li .(pyr)(2)}(2)] 1, [{PhN(H)Li .(4-Me-pyr)(2)}(2)] 2 and [{PhN(H)Li}(4).(4-Bu-t-pyr)(6)] 3 has been synthesised by reacting the aromatic primary amide with two molar equivalents of the appropriate pyridine-based solvent (pyridine, 4-methylpyridine and 4-tert-butylpyridine, respectively) in hexane-toluene solution. X-Ray crystallographic studies have revealed three contrasting structures: 1 adopts a dinuclear, dimeric [(anilido)N-Li](2) ring arrangement with a transoid (anti) conformation of amido substituents; 2 adopts a similar arrangement but with a cisoid (syn) conformation of amido substituents; and 3 adopts a novel tetranuclear arrangement with a central [(anilido)N-Li](2) transoid ring, separating two mixed ligand [(anilido)N-Li-(pyr)N-Li] rings, made possible by the unusual mu-bonding of a 4-tert-butylpyridine ligand. A combination of H-1, Li-7 and C-13 NMR spectroscopic studies at 300 K suggests similar environments exist for corresponding atoms in [H-2(8)]-toluene solutions of 1, 2 or 3. Further examination of the solution of 3 over the temperature window (300-193 K) has detected a fluxional structure involving the intramolecular exchange of two distinct types of anilido ligand, consistent with those present in the molecular structure of crystalline 3.

ORCID iDs

Clegg, W, Horsburgh, L, Liddle, S T, Mackenzie, F M, Mulvey, Robert ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and Robertson, A;
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