Group 11 Metal Complexes Coordinated by the (Nitronyl Nitroxide)-2-ide Radical Anion: Facile Oxidation of Stable Radicals Controlled by Metal-Carbon Bonds in Radical-Metalloids
Group 11 Metal Complexes Coordinated by the (Nitronyl Nitroxide)-2-ide Radical Anion: Facile Oxidation of Stable Radicals Controlled by Metal-Carbon Bonds in Radical-Metalloids
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由(硝硝基氮氧化物)-2-ide自由基阴离子配位的第11族金属配合物：自由基-非金属中金属-碳键控制的稳定自由基的轻松氧化
DOI：
10.1002/ejic.201800038
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发表时间：
2018
影响因子：
2.3
通讯作者：
Okada Keiji
中科院分区：
文献类型：
--
作者：
Tanimoto Ryu;Yamada Kiyomi;Suzuki Shuichi;Kozaki Masatoshi;Okada Keiji
（硝基氮氧化物）- 2 -酰胺自由基NN - M（dtpb）配位的一系列11族金属配合物[NN：硝基氮氧化物]；M: CuI， AgI和AuI；制备了Dtpb: 1,2‐双（二‐2‐甲基磷酰）苯。研究了它们的结构、电化学性能和相关理论计算。与未取代的硝基氮氧化物（NN‐H,Eox= +0.38 V）相比，这些类自由基金属中NN‐部分的氧化电位（Eox, V vs. Fc/Fc+）显著向负方向偏移；这很大程度上取决于金属离子（M = CuI的Eox= -0.37 V， AgI的Eox= -0.31 V， AuI的Eox= -0.28 V）。这些氧值与HOMO （SOMO）的能级相关，也与金属离子上C2碳原子的自然原子电荷相关，表明金属- C2 -碳键的离子特性是控制这些自由基类金属氧化电位的关键因素。
A series of group 11 metal complexes coordinated by (nitronyl nitroxide)‐2‐ide radical anionNN‐M(dtpb)[NN: nitronyl nitroxide; M: CuI, AgI, and AuI; dtpb: 1,2‐bis(di‐2‐tolylphosphanyl)benzene)] was prepared. Their structures, electrochemical properties, and related theoretical calculations were investigated. The oxidation potential (Eox, V vs. Fc/Fc+) of the NN‐moiety in these radical‐metalloids significantly shifted to the negative direction in comparison to that of the unsubstituted nitronyl nitroxide (NN‐H,Eox= +0.38 V); this is strongly dependant on the metal ion (Eox= –0.37 V for M = CuI, –0.31 V for AgI, and –0.28 V for AuI). TheEoxvalues correlated with the energy level of the HOMO (SOMO) and also with the natural atomic charge of the C2 carbon atom attached to the metal ion, indicating that the ionic character of the metal–C2–carbon bond is a key factor in controlling the oxidation potential of these radical metalloids.