By Theilheimer W.
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The exchanging system was simulated as in equation 80. ∗ ∗ −− −− → CLi6 + C∗ Li∗6 − ← − CLi6 + C Li6 (80) Altogether, 728 elements of the density matrix are required. All are off-diagonal in 13 C and diagonal in the states of 6 Li, (equation 81), where ’s are the spin products for the six 6 Li’s (equation 82). α |e|β (81) s=6 = ϕs (82) s=1 The e(ae) elements are obtained as outlined in Section I for a bimolecular exchanging system (equation 83). 1 (e(ae))α ,β = eαm,βm (83) 364 m The 728 elements of the density matrix are simpliﬁed to just 13 unknowns by summing z the elements into groups where the ’s have the same associated i m i = M value (equation 84).
Activation Parameters for rotation in tertiary benzylic lithiumsžTMEDA in isooctane10 X − ...... 5 Too slow to measure. contrast, with p-cyclopropyl the barrier is lower due to ground state destabilization. This system is a vinylogous cyclopropylcarbinyl carbanion. Note the well-known instability of cyclopropylcarbinyl carbanion with respect to rearrangement. Barriers to rotation in conjugated organolithium compounds are strongly dependent on the nature of coordination to lithium. These barriers clearly are not the result of rotation in a carbanion alone.
3 kcal mol−1 and Sin‡ = −3 eu. The structures of the two species could not be identiﬁed from these experiments; both contain delocalized allyl anions. Further, their states of aggregation are different. Some examples which show the dynamic effects of alkyl and silyl substituents on barriers to rotation in allyllithium compounds 26 to 32 are listed in Table 7. These results were obtained from proton NMR line shape data. The procedure for compounds 26, 28, 29 and 32, which exhibited rotation around their C CH2 bonds, is diagrammed by structure 33 in which hydrogens A, B and X are all nonequivalent and each couples to the others.
Synthetische Methoden der Organischen Chemie by Theilheimer W.