Sc3+ 引发 O2 和非血红素铁(II)前体形成 oxoiron(IV)，通过 Sc3+-过氧-Fe3+ 中间产物。
Sc3+-triggered oxoiron(IV) formation from O2 and its non-heme iron(II) precursor via a Sc3+-peroxo-Fe3+ intermediate.
机构信息
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, United States.
出版信息
J Am Chem Soc. 2013 Jul 17;135(28):10198-201. doi: 10.1021/ja402645y. Epub 2013 Jul 2.
Abstract
We report that redox-inactive Sc(3+) can trigger O2 activation by the Fe(II)(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh4(-) as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc(3+) adduct of Fe(III)(η(2)-O2)(TMC) by an alternative route, which was found to have an Fe(3+)-(μ-η(2):η(2)-peroxo)-Sc(3+) core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond cleavage during the course of O2 activation at non-heme iron centers.
摘要
我们报告称，在 BPh4(-)作为电子供体的存在下，氧化还原非活性的 Sc(3+) 可以触发 Fe(II)(TMC)中心（TMC = 四甲基环戊二胺）对 O2 的激活，生成相应的氧代铁(IV)配合物。为了模拟上述反应中的一个可能中间体，我们通过另一种途径生成了前所未有的 Fe(III)(η(2)-O2)(TMC) 的 Sc(3+)加合物，该加合物被发现具有 Fe(3+)-(μ-η(2)：η(2)-过氧)-Sc(3+)核，并转化为氧代铁(IV)配合物。这些结果对于路易斯酸在非血红素铁中心的 O2 激活过程中促进 O-O 键断裂所起的作用具有重要意义。
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