Carbonyl and Benzene Complexes of Lithium: Transition-Metal-Like Behaviour of Lithium in Organolithium Compounds

7Li Solid-state NMR spectroscopic study of aryllithium complexes: effects of aggregation and solvation

“…The solvation can also come from an external benzene solvent molecule. This type of transition metal-like behaviour of lithium has been studied theoretically by Tacke,27 who found that in the absence of Lewis bases, aromatic molecules can act as ligands in organolithium compounds.…”

Cocondensation reactions of heterocyclic aromatic compounds with lithium, calcium and magnesium atoms at 77K

“…Earlier reports involving lithium atoms [4][5][6] showed that they are able to activate aromatic hydrocarbons in the presence of THF selectively under cocondensation conditions at 77 K. This resulted in the direct synthesis of aryl lithium compounds on a synthetic scale. 8LiðgÞ þ 4PhHðgÞ þ 4THFðgÞ !…”

“…However, when 4 was cocondensed, no product could be obtained. The products of these reactions were monocalcium compounds (5)(6)(7) where the heterocyclic ring showed a C-H activation in the ortho position as shown in Scheme 1. In the case of furan, thiophene and methyl pyrrole the yields were 18%, 23% and 8%, respectively.…”

Cocondensation reactions of nitrogen-containing heterocycles with lithium atoms at 77 K

“…Previous reports [4][5][6] showed two different possibilities for the coordination of the dilithium molecule. The first possibility is the coordination of the Li 2 to the aromatic ring to form a p-complex, and the second …”