Diruthenium aryl compounds – tuning of electrochemical responses and solubility
Diruthenium aryl compounds – tuning of electrochemical responses and solubility
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二钌芳基化合物 — 电化学响应和溶解度的调节
DOI：
10.1039/d1dt03957a
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发表时间：
2022
影响因子：
4
通讯作者：
Ren, Tong
中科院分区：
文献类型：
--
作者：
Miller-Clark, Lyndsy A.;Christ, Peter E.;Ren, Tong
本文报道了两个新的钌芳基化合物系列：Ru2(DiMeOap)4(Ar) (1a-6a) （DiMeOap = 2-（3,5-二甲氧基苯基）吡啶）和Ru2(m-iPrOap)4(Ar) (1b-5b) （m-iPrOap = 2-（3-异丙基苯基苯基）吡啶），它们是通过锂-卤素交换反应与多种芳基卤化物(Ar = C6H4-4-NMe2 (1), C6H4-4-tBu (2), C6H4-4-OMe (3), c6h4 -3 -3,5-(OMe)2 (4), C6H4-4-CF3 （5), C6H5(6)）合成的。用x射线衍射法确定了这些化合物的分子结构。此外，利用电子吸收和伏安技术对这些化合物进行了表征。化合物1a-6a和1b-5b均为Ru25+氧化态，基态构型为σ2π4δ2(π*δ*)3 （S = 3/2）。与未取代的Ru2(ap)4(Ar) （ap = 2-苯胺吡啶）系列相比，使用修饰的ap配体（ap '）导致产品收率适度提高。比较了1a-6a和1b-5b与Ru2（ap’）Cl的电化学性能，发现芳基配体的加入使Ru26+/5+氧化电位和Ru25+/4+还原电位发生了阴极位移。这些氧化和还原电位也强烈依赖于轴芳基配体的p取代基。
Reported herein are the two new series of diruthenium aryl compounds: Ru2(DiMeOap)4(Ar) (1a–6a) (DiMeOap = 2-(3,5-dimethoxyanilino)pyridinate) and Ru2(m-iPrOap)4(Ar) (1b–5b) (m-iPrOap = 2-(3-iso-propoxyanilino)pyridinate), prepared through the lithium-halogen exchange reaction with a variety of aryl halides (Ar = C6H4-4-NMe2 (1), C6H4-4-tBu (2), C6H4-4-OMe (3), C6H3-3,5-(OMe)2 (4), C6H4-4-CF3 (5), C6H5 (6)). The molecular structures of these compounds were established with X-ray diffraction studies. Additionally, these compounds were characterized using electronic absorption and voltammetric techniques. Compounds 1a–6a and 1b–5b are all in the Ru25+ oxidation state, with a ground state configuration of σ2π4δ2(π*δ*)3 (S = 3/2). Use of the modified ap ligands (ap′) resulted in moderate increases of product yield when compared to the unsubstituted Ru2(ap)4(Ar) (ap = 2-anilinopyridinate) series. Comparisons of the electrochemical properties of 1a–6a and 1b–5b against the Ru2(ap′)Cl starting material reveals the addition of the aryl ligand cathodically shifted the Ru26+/5+ oxidation and Ru25+/4+ reduction potentials. These oxidation and reductions potentials are also strongly dependent on the p-substituent of the axial aryl ligands.