| 초록 |
Acyclic ortho-phenylene bridged bis(anilido-aldimine) compounds, ortho-C6H4{C6H2R2N=CH-C6H4-(H)N(C6H3R'2)}2 and related 30-membered macrocyclic compounds, ortho-C6H4{C6H2R'2N=CH-C6H4-(H)N-C6H2R2}2(ortho-C6H4) are prepared. Successive additions of Me2Zn and SO2 gas to the bis(anilido-aldimine) compounds afford quantitatively dinuclear methylsulfinato zinc complexes, ortho-C6H4{(C6H2R2N=CH-C6H4-N(C6H3R'2))Zn(OS(O)Me)}2 (R = iPr, R' = iPr, 29; R = Et, R' = Et, 30; R = Me, R' = Me, 31; R = Me, R' = iPr, 32; R = Et, R' = Me, 33; R = Et, R' = iPr, 34; R = iPr, R' = Et, 35) and ortho-C6H4{C6H2R'2N=CH-C6H4-N-C6H2R2)Zn(OS(O)Me)}2(ortho-C6H4) (R = Et, R' = Et, 36; R = Me, R' = Me , 37; R = iPr, R' = Me, 38; R = Et, R' = Me, 39; R = Me, R' = iPr, 40). Molecular structures of 34 and 40 are confirmed by X-ray crystallography. Complexes 30-35 show high activity for cyclohexene oxide/CO2 copolymerization at low [Zn]/[monomer] ratio (1:5600), whereas the complex of mononucleating diketiminate, {[(C6H3Et2)N=C(Me)CH=C(Me)N(C6H3Et2)]Zn(OS(O)Et)}2 shows negligible activity in the same condition. Activity is sensitive to the N-aryl ortho-substituents and the highest activity is observed with 32. Turn over number up to 2980 and molecular weight (Mn) up to 284000 are attained with 32 at such a highly diluted condition as [Zn]/[monomer] = 1:17400. Macrocyclic complexes 36-40 show negligible activity for the copolymerization.
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