Bleher Katharina, Comba Peter, Kass Dustin, Ray Kallol, Wadepohl Hubert
Universität Heidelberg, Anorganisch-Chemisches Institut, INF 270, D-69120 Heidelberg, Germany.
Universität Heidelberg, Anorganisch-Chemisches Institut, INF 270, D-69120 Heidelberg, Germany; Universität Heidelberg, Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), Germany.
J Inorg Biochem. 2023 Apr;241:112123. doi: 10.1016/j.jinorgbio.2023.112123. Epub 2023 Jan 9.
The FeO complexes of bispidines (3,7-diazabicyclo[3.3.1]nonane derivatives) are known to be highly reactive oxidants - with the tetradentate bispidine, the so far most reactive ferryl complex has been reported and two isomeric pentadentate ligands also lead to very reactive high-valent oxidants. With a series of 4 new bispidine derivatives we now try to address the question why the bispidine scaffold in general leads to very reactive oxidants and how this can be tuned by ligand modifications. The study is based on a full structural, spectroscopic and electrochemical analysis of the iron(II) precursors, spectroscopic data of the iron(IV)-oxido complexes, a kinetic analysis of the stoichiometric oxidation of thioanisole by five different bispidine‑iron(IV)-oxido complexes and on product analyses of reactions by the five ferryl oxidants with thioanisole, β-methylstyrene and cis-stilbene as substrates.
双吡啶（3,7-二氮杂双环[3.3.1]壬烷衍生物）的FeO配合物是已知的高活性氧化剂——对于四齿双吡啶，已报道了迄今为止反应活性最高的高铁酰基配合物，并且两种异构体五齿配体也能产生反应活性很高的高价态氧化剂。我们现在使用一系列4种新型双吡啶衍生物来试图解决以下问题：为什么双吡啶支架通常会产生反应活性很高的氧化剂，以及如何通过配体修饰来调节这一特性。该研究基于对铁（II）前体的全面结构、光谱和电化学分析、铁（IV）-氧代配合物的光谱数据、5种不同的双吡啶-铁（IV）-氧代配合物对硫代苯甲醚进行化学计量氧化的动力学分析，以及5种高铁酰基氧化剂与硫代苯甲醚、β-甲基苯乙烯和顺式芪作为底物的反应产物分析。
