通过多氧钨酸盐簇的质子耦合电子转移将偶氮苯选择性氢化为氢化偶氮苯。
Selective Hydrogenation of Azobenzene to Hydrazobenzene via Proton-Coupled Electron Transfer from a Polyoxotungstate Cluster.
作者信息
Lu Zhou, Cooney Shannon E, McKone James R, Matson Ellen M
机构信息
Department of Chemistry, University of Rochester, Rochester, New York 14627, United States.
Departments of Chemical and Petroleum Engineering and Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
出版信息
JACS Au. 2024 Mar 21;4(4):1310-1314. doi: 10.1021/jacsau.4c00127. eCollection 2024 Apr 22.
In this report, we describe proton-coupled electron transfer (PCET) reactivity at the surface of the Keggin-type polyoxotungstate cluster [BuN][PWO] () in acetonitrile. Bond dissociation free energies (BDFEs) of the O-H groups generated upon reduction of in the presence of acid are determined through the construction of a potential-p diagram. The surface O-H bonds are found to be weak (BDFE(O-H) < 48 kcal mol), comparable to the BDFE of H. This is consistent with the observed formation of H upon addition of a suitably strong organic acid, HNPh (p = 5.98), to the reduced form of the cluster. The one-electron reduced form of is isolated and used in conjunction with acid to realize the stoichiometric semihydrogenation of azobenzene via PCET from the surface of the reduced cluster.
在本报告中，我们描述了在乙腈中，Keggin型多氧钨酸盐簇[BuN][PWO]（）表面的质子耦合电子转移（PCET）反应活性。通过构建电位-p图，确定了在酸存在下还原时生成的O-H基团的键解离自由能（BDFE）。发现表面O-H键较弱（BDFE(O-H) < 48 kcal mol），与H的BDFE相当。这与在向簇的还原形式中加入适当强的有机酸HNPh（pKa = 5.98）时观察到的H的形成一致。分离出的单电子还原形式与酸一起使用，通过还原簇表面的PCET实现偶氮苯的化学计量半氢化。
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