含鎳超氧化物歧化酶擬態化合物之合成
Abstract
本研究承接本實驗室所開發出的鎳超氧岐化酶擬態化合物2,6-bis(((S)-2-(diphenyl-hydroxymethyl)-1pyrrolidinyl)methyl)pyridine (H2BDPP)系列配基，將苯環區進行修飾得到H2BDP2-dioP。此配基在進行去質子化後與[Ni(CH3CN)6](ClO4)2反應得到的二價錯合物Ni(BDP2-dioP)，可跟氧化劑反應得到三價鎳的EPR光譜，從UV-vis光譜上也可以看到此三價鎳錯合物與超氧化鉀反應還原成二價NiBDP2-dioP的過程。除了如同其他NiBDPP系列錯合物一般有形成鎳三價錯合物的特性。在不破壞配位中心的條件下，Ni(BDP2-dioP)可以直接進行官能基轉換形成醛基修飾鎳二價錯合物NiBDPCHOP。基於醛類易氧化還原與跟其他官能基縮合等特點，提供Ni(BDPCHOP)進一步進行官能基修飾，和接到胜肽鏈上合成人工酵素的潛力
Based on the ligand 2,6-bis(((S)-2-(diphenyl-hydroxymethyl)-1-pyrrolidinyl)methyl)pyridine (H2BDPP) previously synthesized in our lab, this work has focused on studying that how to change a functonal group to another on the ligand in the mimics of NiSOD. Therefore, we have designed and synthsized a protected ligand H2BDP2-dioP. After deprotonating the ligands and reacting with [Ni(CH3CN)6](ClO4)2, the complexe Ni(BDP2-dioP) (1) have been prepared. Complex 1 can be oxided by FcPF6 to [Ni(BDP2-dioP)](PF6) (3), which has been demonstrated by the EPR diagrams to NiIII species. The electron absorption spectroscopy and X-ray crystallography indicate that reaction of 3 with KO2 produce original complexes 1 without deprotection of dioxolane group. The dioxolane group of complex 1 is stable unless it has been deprotected by FeCl3 to Ni(BDPCHOP) (2), without side reaction and demetalation.
Based on the ligand 2,6-bis(((S)-2-(diphenyl-hydroxymethyl)-1-pyrrolidinyl)methyl)pyridine (H2BDPP) previously synthesized in our lab, this work has focused on studying that how to change a functonal group to another on the ligand in the mimics of NiSOD. Therefore, we have designed and synthsized a protected ligand H2BDP2-dioP. After deprotonating the ligands and reacting with [Ni(CH3CN)6](ClO4)2, the complexe Ni(BDP2-dioP) (1) have been prepared. Complex 1 can be oxided by FcPF6 to [Ni(BDP2-dioP)](PF6) (3), which has been demonstrated by the EPR diagrams to NiIII species. The electron absorption spectroscopy and X-ray crystallography indicate that reaction of 3 with KO2 produce original complexes 1 without deprotection of dioxolane group. The dioxolane group of complex 1 is stable unless it has been deprotected by FeCl3 to Ni(BDPCHOP) (2), without side reaction and demetalation.
Description
Keywords
鎳錯合物, 含鎳超氧化物歧化酶, 擬態化合物, Ni Complexs, NiSOD, Mimics