Internally solvated cyclopentadienyllithium compounds: structural integrity of the Cp-Li+ moiety. NMR, dynamics, X-ray crystallography, and calculations

Structure: see text]. N(CH2CH2OCH3)2 are as follows: T = CHCH(CH3)2, 6; T = (CH2)2, 10; T = (CH2)3, 14. The results of NOE NMR experiments for 6, 10, and 14 together with X-ray crystallography of 14 support internally coordinated monomeric structures for all three compounds. Models have been constructed for 6, 10, and 14 from modifications of an internally solvated allylic lithium compound at the B3LYP level of theory using basis set 6-311G*. The resulting structural features are very similar to those obtained from the NMR and crystallographic data. In addition, 13C NMR shifts obtained with the GIAO procedure using the results of the B3LYP/6-311G* calculations are closely similar to the experimental shifts, which validate B3LYP as a suitable model for these compounds. The Li+ centroid distance of ca. 1.9 A to 2.0 A obtained for 6, 10, and 14 is common to most crystallographic data for externally solvated Cp-Li+ compounds as well as one which incorporates a (CpLiCp)- triple ion. It is concluded that the ligand tether and the stereochemistry around Li+ accommodate to maintain the structural integrity of Cp-Li+. NMR and crystallography show 14 to be chiral. Carbon-13 NMR line shape changes are attributed to inversion via a lateral wobble mechanism with DeltaH++ = 6 kcal x mol(-1) and DeltaS++ = -2 eu. It is also shown that a 6,6-dimethylfulvene is deprotonated at methyl by LiN(CH2CH2OCH3)3 as well as by butyllithium in the presence of PMDTA producing isopropenyl Cp-Li+ compounds 24 and 25, respectively. NMR line shape changes of the sample containing 24 have been qualitatively interpreted to result from a combination of fast transfer of coordinated ligand between faces of the carbanion plane as well as a lithium-exchange process.