Lithiated Hydrocarbons, Their Conjugate Bases, and Corresponding Radicals: A Computational Study of RLi (R = CH3, CH3CH2, CH2=CH, and HC≡C)

Lawrence M. Pratt, Steven R Kass

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Abstract

Organolithium compounds RLi (R = CH3, CH3CH 2, CH2=CH, and HC≡C) and their corresponding hydrocarbons were fully optimized at the MP2/6-311+G(2df,2pd) level. Single-point energy calculations also were carried out at the CCSD(T) and B3LYP levels with the same triple split-valence basis set. Acidities, electron affinities, and bond dissociation energies are reported, and the following general results were found: (1) α-Lithio anions are ground-state triplet molecules. (2) Lithium is an acid-enhancing substituent. (3) Conjugate bases of organolithiums are stable with respect to electron loss and therefore are attractive targets for mass spectrometry investigations. (4) Lithium weakens α- and β-C-H bonds, the latter by ∼25 kcal mol-1. Consequently, radical chemistry of lithiated compounds at remote sites is a promising area for exploration.

Original languageEnglish (US)
Pages (from-to)2123-2127
Number of pages5
JournalJournal of Organic Chemistry
Volume69
Issue number6
DOIs
StatePublished - Mar 19 2004

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