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螯合的[Zn(环胺)]路易斯酸提高了含庞大联吡啶配体的锰催化剂对CO电化学还原的反应活性。

Chelated [Zn(cyclam)] Lewis acid improves the reactivity of the electrochemical reduction of CO by Mn catalysts with bulky bipyridine ligands.

作者信息

Zhanaidarova Almagul, Steger Han, Reineke Mark H, Kubiak Clifford P

机构信息

Department of Chemistry and Biochemistry, University of California San Diego, 9500 Gilman Drive MC 0358, La Jolla, California 92093, USA.

出版信息

Dalton Trans. 2017 Sep 26;46(37):12413-12416. doi: 10.1039/c7dt02620j.

Abstract

This communication reports the use of a soluble Lewis acid complex, [Zn(cyclam)] (cyclam = 1,4,8,11-tetraazacyclotetradecane) as a co-catalyst coupled with Mn(Mesbpy)(CO)Br (Mesbpy = 6,6'-dimesityl-2,2'-bipyridine) for the electrochemical reduction of CO to CO. Utilization of the soluble chelated Lewis acid avoids the use of sacrificial additives and prevents the formation of insoluble products such as MgCO or ZnCO that change the thermodynamics of CO reduction. The use of soluble Lewis acids greatly improves catalysis compared to previously reported systems that used sacrificial anodes.

摘要

本通讯报道了使用可溶性路易斯酸配合物[Zn(环胺)](环胺=1,4,8,11-四氮杂环十四烷)作为助催化剂,与Mn(间甲基联吡啶)(CO)Br(间甲基联吡啶=6,6'-二间甲基-2,2'-联吡啶)耦合用于将CO电化学还原为CO。使用可溶性螯合路易斯酸避免了使用牺牲添加剂,并防止了不溶性产物如MgCO或ZnCO的形成,这些产物会改变CO还原的热力学。与先前报道的使用牺牲阳极的体系相比,可溶性路易斯酸的使用极大地改善了催化作用。

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