Lee Bun Yeoul, Kwon Heon Yong, Lee Su Yeon, Na Sung Jae, Han Song-I, Yun Hoseop, Lee Hyosun, Park Young-Whan
Department of Molecular Science and Technology, Ajou University, Suwon 443-749 Korea.
J Am Chem Soc. 2005 Mar 9;127(9):3031-7. doi: 10.1021/ja0435135.
Acyclic o-phenylene-bridged bis(anilido-aldimine) compounds, o-C(6)H(4){C(6)H(2)R(2)N=CH-C(6)H(4)-(H)N(C(6)H(3)R'(2))}(2) and related 30-membered macrocyclic compounds, o-C(6)H(4){C(6)H(2)R'(2)N=CH-C(6)H(4)-(H)N-C(6)H(2)R(2)}(2) (o-C(6)H(4)) are prepared. Successive additions of Me(2)Zn and SO(2) gas to the bis(anilido-aldimine) compounds afford quantitatively dinuclear mu-methylsulfinato zinc complexes, o-C(6)H(4){(C(6)H(2)R(2)N=CH-C(6)H(4)-N(C(6)H(3)R'(2))-kappa(2)-N,N)Zn(mu-OS(O)Me)}(2) (R = iPr and R' = iPr, 29; R = Et and R' = Et, 30; R = Me and R'= Me, 31; R = Me and R' = iPr, 32; R = Et and R' = Me, 33; R = Et and R' = iPr, 34; R = iPr and R' = Et, 35) and o-C(6)H(4){C(6)H(2)R'(2)N=CH-C(6)H(4)-N-C(6)H(2)R(2)-kappa(2)-N,N)Zn(mu-OS(O)Me)}(2) (o-C(6)H(4)) (R = Et and R'= Et, 36; R = Me and R' = Me, 37; R = iPr and R' = Me, 38; R = Et and R' = Me, 39; R = Me and R'= iPr, 40). Molecular structures of 34 and 40 are confirmed by X-ray crystallography. Complexes 30-35 show high activity for cyclohexene oxide/CO(2) copolymerization at low [Zn]/[monomer] ratio (1:5600), whereas the complex of mononucleating beta-diketiminate {[(C(6)H(3)Et(2))N=C(Me)CH=C(Me)N(C(6)H(3)Et(2))]Zn(mu-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. Turnover number up to 2980 and molecular weight (M(n)) up to 284 000 are attained with 32 at such a highly diluted condition as [Zn]/[monomer] = 1:17 400. Macrocyclic complexes 36-40 show negligible activity for copolymerization.
制备了无环邻亚苯基桥连双（苯胺基 - 醛亚胺）化合物o - C(6)H(4){C(6)H(2)R(2)N = CH - C(6)H(4)-(H)N(C(6)H(3)R'(2))}(2)以及相关的30元大环化合物o - C(6)H(4){C(6)H(2)R'(2)N = CH - C(6)H(4)-(H)N - C(6)H(2)R(2)}(2)（o - C(6)H(4)）。向双（苯胺基 - 醛亚胺）化合物中依次加入二甲基锌和二氧化硫气体，定量得到双核μ - 甲基亚磺酰锌配合物o - C(6)H(4){(C(6)H(2)R(2)N = CH - C(6)H(4)-N(C(6)H(3)R'(2)) - κ(2)-N,N)Zn(μ - OS(O)Me)}(2)（R = 异丙基且R' =异丙基，29；R = 乙基且R' = 乙基，30；R = 甲基且R' = 甲基，31；R = 甲基且R' = 异丙基，32；R = 乙基且R' = 甲基，33；R = 乙基且R' = 异丙基，34；R = 异丙基且R' = 乙基，35）和o - C(6)H(4){C(6)H(2)R'(2)N = CH - C(6)H(4)-N - C(6)H(2)R(2)-κ(2)-N,N)Zn(μ - OS(O)Me)}(2)（o - C(6)H(4)）（R = 乙基且R' = 乙基，36；R = 甲基且R' = 甲基，37；R = 异丙基且R' = 甲基，38；R = 乙基且R' = 甲基，39；R = 甲基且R' = 异丙基，40）。通过X射线晶体学确定了34和40的分子结构。配合物30 - 35在低[Zn]/[单体]比（1:5,600）下对环氧环己烷/二氧化碳共聚显示出高活性，而单核β - 二酮亚胺配合物{[(C(6)H(3)Et(2))N = C(Me)CH = C(Me)N(C(6)H(3)Et(2))]Zn(μ - OS(O)Et)}(2)在相同条件下活性可忽略不计。活性对N - 芳基邻位取代基敏感，32表现出最高活性。在[Zn]/[单体] = 1:17,400这样的高度稀释条件下，32的周转数高达2,980，分子量（M(n)）高达284,000。大环配合物36 - 40对共聚显示出可忽略不计的活性。
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