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Updated: Jun 9, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Insights into [(2-phen-oxy-phen-yl)lithium(THF)(TMEDA)] and diphenyl ether: structural influence of metalation on the
Michael Nuss1, Tobias Schrimpf1, Carsten Strohmann1
1Technische Universität Dortmund, Fakultät Chemie und Chemische Biologie, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany.
Abstract:
The title compound, (2-phen-oxy-phenyl-κC 1)(tetra-hydro-furan-κO)(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ2 N,N')lithium, [Li(C12H9O)(C6H16N2)(C4H8O)] or [(2-phen-oxy-phen-yl)lithium(THF)(TMEDA)], (1), is a monomeric lithium complex in which tetra-hydro-furan (THF) and N,N,N',N'-tetra-methyl-ethylenedi-amine (TMEDA) play essential roles in stabilizing the lithium ion and promoting a monomeric aggregate. This stabilization allows the lithium cation to maintain a distorted tetra-hedral coordination environment, which enhances its reactivity in organometallic chemistry. Organolithium species, particularly in combination with TMEDA and THF, are widely used in synthetic organic chemistry for deprotonation and metalation reactions due to their strong nucleophilic and basic properties. The structure of compound 1, [Li(C12H9O)(C6H16N2)(C4H8O)]·0.212[C5H12]·0.2[C5H12], was determined at 100 K and crystallizes in the triclinic space group P1. The structure exhibits disorder of the coordinating THF ligand as well as disordered solven, which was modeled using a split model. In addition, disordered co-crystallized n-pentane was treated using the OLEX2 solvent-mask procedure. For comparison, diphenyl ether (2), C12H10O, was also redetermined at 100 K and refined using SHELXL. It crystallizes in the ortho-rhom-bic space group P212121. This redetermination enables a direct and consistent comparison between educt and product and highlights the influence of li-thia-tion on structural properties. The structure of diphenyl ether corresponds to the literature-known polymorph II reported by Choudhury et al. [(2004). J. Am. Chem. Soc. 126, 12274-12275; CSD code: RAFFIO], and serves as a reliable reference for structural comparison.
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