E. Anders et al., PICOLINE AND TOLUENE - A COMPARISON OF STRUCTURAL-PROPERTIES AND RELATIVE STABILITIES OF THEIR MONOLITHIATED DERIVATIVES, Journal of organic chemistry, 58(16), 1993, pp. 4424-4430
Energy differences between five isomeric monolithiated 4-picolines 6a
(eta3 at Calpha/C4/C3), 6b (eta5 at Nl/C2/C3/C6/C5), 6c (eta2 at Calph
a/C4), 6da (N1-lithiated), and 6e (eta3 at C3/C4/C5) were calculated b
y ab initio (MP2/6-31+G//6-31G*) and semiempirical (MNDO) methods. Wi
th this basis set and inclusion of the ZPE correction, 6a-c and 6e tur
n out to be quite close in energy (within 0.13 kcal mol-1). 6c and 6e
are transition structures. The N-lithiated structure 6da is least stab
le (about 5.5 kcal mol-1, compared with the above compounds). MNDO ove
remphasizes the instability of 6da by about 11 to 16 kcal mol-1. Howev
er, the ab initio calculated structural parameters of the anionic part
of Gda compare quite well with those of a model of a ''dimeric'' stru
cture 8, in which the 4-picolyl and the NH2 anion are arranged in the
characteristic lithium-bridged bis-amide fashion as found, e.g., for [
LDA(TMEDA)]2 complexes. Furthermore, the heterocyclic moiety of the mo
del compounds 8 and 6da reveal significant similarities to X-ray struc
tural data of closely related [{4-(CH3CRCH3)-C5H4N}Li(TMEDA or (THF)2)
]2 complexes (R = H, CH3) 3,4a, and 4b. TMEDA or THF coligands almost
do not influence the structural parameters of the anionic part. Theref
ore, 6da and the Calpha-substituted models [4-(CH3CRC5H4N)Li (6db: R =
H, 6dc: R = CH3), which are accessible to reliable ab initio calculat
ions, represent the most simplified structures to describe this part o
f such complexes adequately. Similar aspects for the interpretation of
a variety of known benzyllithium X-ray structures (which differ in th
e nature of the coligands involved) are found by calculating the four
analogous ''pi-eta'' isomers la,b. In this context, MNDO should be use
d with caution, as relative stabilities and activation barriers disagr
ee significantly with high level ab initio calculations. In contrast t
o MP2/6-31+G//6-31G* calculations, MNDO predicts ortho-lithiated tolu
ene 7 to be more stable than la,b.