A series of group 11 metal complexes coordinated by (nitronyl nitroxide)‐2‐ide radical anion NN‐M(dtpb) [NN: nitronyl nitroxide; M: Cu^I, Ag^I, and Au^I; dtpb: 1,2‐bis(di‐2‐tolylphosphanyl)benzene)] was prepared. Their structures, electrochemical properties, and related theoretical calculations were investigated. The oxidation potential (E_ox, 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, E_ox = +0.38 V); this is strongly dependant on the metal ion (E_ox = –0.37 V for M = Cu^I, –0.31 V for Ag^I, and –0.28 V for Au^I). The E_ox values 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.

中文翻译：

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由（硝基亚硝基氧）-2-离子自由基阴离子配位的第11组金属配合物：自由基-金属中金属-碳键控制的稳定自由基的容易氧化

一系列11族金属配合物，由（亚硝酰基氮氧化物）-2-离子自由基阴离子NN-M（dtpb）配位[NN：硝酰基氮氧化物; M：Cu ^I，Ag ^I和Au ^I；dtpb：制备了1,2-双（二-2-甲苯基膦基苯））。研究了它们的结构，电化学性能以及相关的理论计算。与未取代的硝酰氮氧化物（NN-H，E _ox = +0.38）相比，这些自由基-准金属中NN-基团的氧化电势（E _ox，V vs. Fc / Fc ⁺）显着向负方向移动。V）; 这在很大程度上取决于金属离子（E _ox对于M = Cu ^I = –0.37 V，对于Ag ^I = –0.31 V，对于Au ^I = –0.28 V ）。所述Ë_牛与HOMO（SOMO）的能量水平相关，并且还与自然原子电荷附着在金属离子的C2碳原子的值，这表明金属-C2 -碳键的离子特性是一个关键因素在控制这些自由基准金属的氧化电位中。