| Abstract: | Proton-hyperfine data are reported for the radical anions generated from azulene ( 1 ) and its alkyl derivatives 2 – 11 in 1,2-dimethoxyethane both ‘chemically’ with K and electrolytically. The alkyl derivatives are 1,3-dimethyl- ( 2 ), 5,7-dimethyl- ( 3 ), 1,3,5,7-tetramethyl- ( 4 ), 2-methyl- ( 5 ), 4,6,8-trimethyl- ( 6 ), 2,4,6,8-tetramethyl-( 7 ), 1,3,4,6,8-pentamethyl- ( 8 ), 1,3,4,8-tetramethyl-6-propyl- ( 9 ), 6-(tert-butyl)-1,3,4,8-tetramethyl- ( 10 ), and 1,2,3,4,6,8-hexamethylazulene ( 11 ). Alkyl substituents at the odd-numbered centers μ = 1, 3, 5, and 7 partly shift the π-spin population from the seven- to the five-membered ring, whereas those at the even-numbered centers μ = 4, 6, and 8 exert an opposite effect on the π-spin distribution. |
