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首页> 外文期刊>Inorganic Chemistry Communications >Phosphate diester hydrolysis promoted by Zinc(II)complexes with alkoxide pendants
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Phosphate diester hydrolysis promoted by Zinc(II)complexes with alkoxide pendants

机译:锌(II)与醇盐侧基配合物促进的磷酸二酯水解

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摘要

Two new Zn(II)complexes of tripodal pyridyl-amine ligands with alcohol pendants,2-[bis-(2-pyridin-2-yl-ethyl)-amino]-ethanol(L~1)and 3-[bis-(2-pyridin-2-yl-ethyl)-amino]-propan-1-ol(L~2),have been synthesized and structurally characterized.The reactivities of ZnL~1(1)and ZnL~2(2)for promoting the hydrolysis of bis(p-nitrophenyl)phosphate(BNPP)have been investigated,and both complexes are highly active in catalyzing the hydrolysis of BNPP,with 2(k = 1.8 x 10~(-1)M~(-1)s~(-1))being about two orders of magnitude more active than 1(k = 2.7 x 10~(-3)M~(-1)s~(-1))in promoting the hydrolysis of BNPP.The differences in reactivity can be attributed to the disparate abilities of the alkoxide nucleophiles in the pendant groups in ligands L~1 and L~2 to attack the substrate phosphate diester BNPP due to differences in their tether lengths.X-ray crystal structures of 1 and 2 are also reported,which show that the complexes form dimers with bridging alkoxide ligands in the solid state.
机译:具有醇侧基的三脚架吡啶胺配体的两个新的Zn(II)配合物,2- [双-(2-吡啶-2--2-乙基-乙基)-氨基]-乙醇(L〜1)和3- [双-(合成了2-吡啶-2-基-乙基-氨基)-丙-1-醇(L〜2)并进行了结构表征.ZnL〜1(1)和ZnL〜2(2)的反应活性研究了双(对硝基苯基)磷酸酯(BNPP)的水解反应,两种配合物在催化2(k = 1.8 x 10〜(-1)M〜(-1)s时都具有很高的催化活性。 〜(-1))在促进BNPP水解方面的活性比1(k = 2.7 x 10〜(-3)M〜(-1)s〜(-1))高约两个数量级。反应性可归因于配体L〜1和L〜2的侧基中的醇盐亲核体具有不同的束缚长度,因为它们的系链长度不同,它们攻击底物磷酸二酯BNPP的能力.X和1的X射线晶体结构是也报道了,这表明该络合物与固态的桥连醇盐配体形成二聚体。

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