Interaction of the 2-(phenyl-2-ol)-6-ketiminopyridines 2-(4′-R 1 -C 6 H 3 -2′-OH)-6-{CMeN(2″,6″-i-Pr 2 C 6 H 3 )}C 5 H 3 N (R 1 = H (L1 a -H), Bu t (L1 b -H), Cl (L1 c -H), F (L1 d -H)) with AlMe 3 at elevated temperature and subsequent crystallization from acetonitrile affords the five-coordinate 2-(phenyl-2-olate)-6-(2-amidoprop-2-yl)pyridine aluminum− methyl complexes [2-(4′-R 1 C 6 H 3 -2′-O)-6-{CMe 2 N(2″,6″-i-Pr 2 C 6 H 3 )}C 5 H 3 N]AlMe(NCMe) (R 1 = H (1a), Bu t (1b), Cl (1c), F (1d)), as their acetonitrile adducts, in good yield. In each case, complexation results in concomitant C−C bond formation via methyl migration from aluminum to the corresponding imino unit in L1-H. On the other hand, reactions of the aldimine-containing compounds 2-, in which the migrated methyl group and aluminum−methyl are disposed mutually cis; evidence for the minor trans isomers 2a′−c′ is presented. The ring-opening polymerization of ε-caprolactone employing 1 and 2 in the presence of PhCH 2 OH proceeded efficiently, producing polymers of narrow molecular weight distribution with the catalytic activities highly dependent on the nature of the phenolate-containing 4-R 1 substituent with the F and Bu t initiators showing the highest activities (1b ≈ 1d > 1a ≈ 1c and 2b > 2a > 2c); in general the CMe 2 -containing series 1 were more active than CH(Me)-containing 2 at 30 °C. The bimetallic complex [{2-(4′-Bu t -C 6 H 3 -2′-O)-6-{CHMeN(2″,6″-i-Pr 2 C 6 H 3 )}C 5 H 3 N}AlMe(μ-OMe)AlMe 2 ] (3), the result of adventitious oxygenation, is also reported. The single-crystal X-ray structures are reported for L1 d -H, L1 f -H, 1a−d, 2a, 2b/2b′, 2c, and 3.
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