A homologous series of electronically tuned 2,2′,2′′-nitrilotris(N-arylacetamide) pre-ligands (H₃L^R) were prepared (R = NO₂, CN, CF₃, F, Cl, Br, Et, Me, H, OMe, NMe₂) and some of their corresponding Fe and Zn species synthesized. The iron complexes react rapidly with O₂, the final products of which are diferric mu-oxo bridged species. The crystal structure of the oxidized product obtained from DMA solutions contain a structural motif found in some diiron proteins. The mechanism of iron mediated O₂ reduction was explored to the extent that allowed us to construct an empirically consistent rate law. A Hammett plot was constructed that enabled insightful information into the rate-determining step and hence allows for a differentiation between two kinetically equivalent O₂ reduction mechanisms.

中文翻译：

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用电子可调非血红素铁酶模型复合物解释 O ₂还原的机理†

制备了一系列电子调谐的2,2 '，2 ''-硝腈（N-芳基乙酰胺）预配体（H ₃ L ^R）的同源物（R = NO ₂，CN，CF ₃，F，Cl，Br，Et ，Me，H，OMe，NMe ₂）及其一些相应的Fe和Zn物种合成。铁络合物与O ₂迅速反应，O ₂的最终产物是二铁mu-oxo桥联物种。从DMA溶液获得的氧化产物的晶体结构包含一些二铁蛋白中发现的结构基序。铁介导的O ₂的作用机理在一定程度上探讨了降低率，使我们能够建立一个经验上一致的利率定律。构造了Hammett图，该图使能见识的信息进入速率确定步骤，因此可以区分两个动力学等效的O ₂还原机理。