一种用于非血红素铁促进烯烃氧化的变色龙催化剂。
A chameleon catalyst for nonheme iron-promoted olefin oxidation.
作者信息
Iyer Shyam R, Javadi Maedeh Moshref, Feng Yan, Hyun Min Young, Oloo Williamson N, Kim Cheal, Que Lawrence
机构信息
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, USA.
出版信息
Chem Commun (Camb). 2014 Nov 18;50(89):13777-80. doi: 10.1039/c4cc06164k.
We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.
我们报道了两种非血红素铁催化剂用于过氧化氢烯烃氧化反应时呈现的变色龙式反应活性，即在加入乙酸后，反应从主要对贫电子烯烃进行顺式二羟基化转变为主要对富电子烯烃进行环氧化。这种转变表明，亲核氧化剂（推测为Fe(III)-η(2)-OOH）和亲电氧化剂（推测为Fe(V)(O)(OAc)）存在一个共同的前体，且乙酸的可逆配位是一种转变途径。
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