Arylallylic lithium compounds, internally versus externally coordinated: comparison of their structures and dynamic behavior via X-ray crystallography and NMR.

A comparison of externally coordinated arylallyllithiums with internally coordinated arylallyllithiums using a combination of X-ray and NMR studies shows that 2-bis(2-methoxyethyl)aminomethyl-1-phenyla-llyllithium 7, and 2-bis(2-methoxyethyl)aminomethyl-1,3-diphenylailyllithi um 8, are indeed fully internally coordinated with all phenyls endo, and lithium is close to one terminal allyl carbon. By contrast, among the externally coordinated analogs 1-phenylallyl-lithium.(HMPT)(4) 5, and 1-phenylailyllithium.(THF) 6, both phenyls are exo and the proximity of lithium to anion was only detected in compound 6. Lithium-7 NMR clearly identifies the Li(HMPT)(4)(+) complex in 5, whereas a Li-7{H-1} HOESY experiment reveals Li-7 to be coordinated to THF in 6 and close to the PhC terminal allyl carbon. Carbon-13 NMR shows that all of the above compounds are fully delocalized despite differences among the sites of lithium and their separations from the anions. Changes in the C-13 NMR line shapes show that the diphenyl compound 8 undergoes a very fast 1,3-lithium sigmatropic shift, and all of the phenyls in the above compounds undergo fast rotation around their phenyl C-ipso-C-allyl, bonds. Barriers to rotation, Delta H-double dagger from NMR line shapes for 5, 6, 7, and 8 respectively, are 19.8, 14.6, 10.2, and 8.9 kcal.mol(-1). The decrease in barriers is clearly correlated with a decrease in separation of lithium from an allyl terminal carbon and implies that especially among the latter three, 6, 7, and 8, lithium is involved in the mechanism for phenyl rotation. This question is discussed.