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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Homoleptic aminophenolates of Zn, Mg and Ca. Synthesis, structure, DFT studies and polymerization activity in ROP of lactides
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Homoleptic aminophenolates of Zn, Mg and Ca. Synthesis, structure, DFT studies and polymerization activity in ROP of lactides

机译：Zn，Mg和Ca的同质氨基酚盐。丙交酯的ROP合成，结构，DFT研究和聚合活性

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摘要

The reaction of MgBu_2, ZnEt_2 or Ca(OiPr)_2 with 2 eq. of three-coordinating N-[methyl(2-hydroxy-3,5- dimethylphenyl)]-N-methyl-N-methyl-1,3-oxolaneamine (mpoa-H) or N-[methyl(2-hydroxy-3,5-di-tertbutylphenyl)]- N-methyl-N-methyl-1,3-oxolaneamine (tbpoa-H) gave neutral, monomeric [Mg(mpoa)_2], [Zn(mpoa)_2], [Zn(tbpoa)_2], and [Ca(tbpoa)_2] as white powders in 58-90% yields. The resulting aminophenolates were characterized in solution by NMR showing, in the case of [Zn(tbpoa)_2], interesting dynamics. [Zn(tbpoa)_2] and [Ca(tbpoa)_2] were characterized by X-ray crystallography to show the Zn atom to be pseudo-octahedrally coordinated and the Ca atom in six-coordination mode. The new homoleptic complexes were tested in the polymerization of lactide with an external alcohol to reveal stable behaviour (during the polymerization process) only in the case of [Zn(tbpoa)_2]. The high activity of the catalyst was correlated with a ligand flexibility that was further supported by theoretical studies.
机译：MgBu_2，ZnEt_2或Ca（OiPr）_2与2 eq。的反应三配位N- [甲基（2-羟基-3,5-二甲基苯基）]-N-甲基-N-甲基-1,3-氧戊胺（mpoa-H）或N- [甲基（2-羟基-3） ，5-二叔丁基苯基）]-N-甲基-N-甲基-1,3-氧戊烷胺（tbpoa-H）得到中性单体[Mg（mpoa）_2]，[Zn（mpoa）_2]，[Zn（ tbpoa）_2]和[Ca（tbpoa）_2]白色粉末，产率58-90％。所得氨基酚盐在溶液中通过NMR表征，在[Zn（tbpoa）_2]情况下，显示出令人感兴趣的动力学。通过X射线晶体学表征[Zn（tbpoa）_2]和[Ca（tbpoa）_2]，显示Zn原子为准八面体配位且Ca原子为六配位模式。仅在[Zn（tbpoa）_2]的情况下，才在丙交酯与外部醇的聚合反应中测试了新的均聚物络合物，以显示稳定的行为（在聚合过程中）。催化剂的高活性与配体的柔韧性相关，理论研究进一步证实了这种配体的柔韧性。

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