Hangman Corroles: Efficient Synthesis and Oxygen Reaction Chemistry
Hangman Corroles: Efficient Synthesis and Oxygen Reaction Chemistry
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DOI：
10.1021/ja108904s
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发表时间：
2011-01-12
影响因子：
15
通讯作者：
Nocera, Daniel G.
中科院分区：
文献类型：
--
作者：
Dogutan, Dilek K.;Stoian, Sebastian A.;Nocera, Daniel G.
一类新的化合物--绞刑者腐蚀物--的构造是通过由联苯进行的大环生成反应的修饰而有效地提供的。绞刑式钴腐蚀剂是通过一锅缩合二吡咯甲烷与黄杂环的醛，然后使用微波辐射插入金属而提供的。在高氧化态下，氯离子配位钴的X-带EPR谱和密度泛函理论计算结果与Co(III)中心在单电子氧化后的大环中的描述一致。这些高氧化态很可能是在O-O键的活化过程中进入的。沿着这些思路，我们证明了HAXMAN平台上的质子供体基团与CoRole的氧化还原性质协同作用，从而提高了O-O键的催化活性。与未经修饰的腐蚀剂相比，绞刑器腐蚀剂显示出更强的选择性将氧气还原为水的活性。氧还原前的氧加合物用电子顺磁共振和吸收光谱进行了表征。
The construction of a new class of compounds-the hangman corroles-is provided efficiently by the modification of macrocyclic forming reactions from bilanes. Hangman cobalt corroles are furnished in good yields from a one-pot condensation of dipyrromethane with the aldehyde of a xanthene spacer followed by metal insertion using microwave irradiation. In high oxidation states, X-band EPR spectra and DFT calculations of cobalt corrole axially ligated by chloride are consistent with the description of a Co(III) center residing in the one-electron oxidized corrole macrocycle. These high oxidation states are likely accessed in the activation of O-O bonds. Along these lines, we show that the proton-donating group of the hangman platform works in concert with the redox properties of the corrole to enhance the catalytic activity of O-O bond activation. The hangman corroles show enhanced activity for the selective reduction of oxygen to water as compared to their unmodified counterparts. The oxygen adduct, prior to oxygen reduction, is characterized by EPR and absorption spectroscopy.