Amine- and ether-chelated aryllithium reagents-structure and dynamics

Chelation and aggregation in phenyllithium reagents with potential 6- and 7-ring chelating amine (2, 3) and 5-, 6-, and 7-ring chelating ether (4, 5, 6) ortho substituents have been examined utilizing variable temperature Li-6 and C-13 NMR spectroscopy, Li-6 and N-15 isotope labeling, and the effects of solvent additives. The 5- and 6-ring ether chelates (4, 5) compete well with THF, but the 6-ring amine chelate (2) barely does, and 7-ring amine chelate (3) does not. Compared to model compounds (e.g., 2-ethylphenyllithium 7), which are largely monomeric in THF, the chelated compounds all show enhanced dimerization (as measured by K=[D]/[M](2)) by factors ranging from 40 (for 6) to more than 200 000 (for 4 and 5). Chelation isomers are seen for the dimers of 5 and 6, but a chelate structure could be assigned only for 2-(2-dimethylaminoethyl)phenyllithium (2), which has an A-type structure (both amino groups chelated to the same lithium in the dimer) based on NMR coupling in the N-15, Li-6 labeled compound. Unlike the dimer, the monomer of 2 is not detectably chelated. With the exception of 2-(methoxymethyl)phenyl lithium (4), which forms an open dimer (12) and a pentacoordinate monomer (13), the lithium reagents all form monomeric nonchelated adducts with PMDTA.