An NMR study of the rotational barriers in cobalt-stabilized carbocations: X-ray crystal structures of (η4-C4Ph4)Co-(η5-C5H4R), where R is CH3CO, CHO, CH(tBu)OH

Treatment of the aldehyde (η4-C4Ph4)Co(η5-C5H4-CHO) (4b) with tert-butyllithium or phenyllithium yields the secondary alcohols (η4-C4Ph4)Co(η5-C5H4-CH(R)OH), where R=tert-butyl (5) or phenyl (6). Protonation of 5 and 6 at −80 °C furnishes the deep purple, cobalt-stabilized cations, 7 and 8, respectively, both of which exhibit restricted rotation about the external C5H4–CHR+ linkage on the NMR time-scale. These data indicate a minimum value for …