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A Contrasting Effect of Acid in Electron Transfer, Oxygen Atom Transfer, and Hydrogen Atom Transfer Reactions of a Nickel(III) Complex
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-11-29 , DOI: 10.1021/acs.inorgchem.2c02504
Jisheng Zhang 1 , Yong-Min Lee 1 , Mi Sook Seo 1 , Madhuri Nilajakar 1 , Shunichi Fukuzumi 1 , Wonwoo Nam 1
Affiliation  

There have been many examples of the accelerating effects of acids in electron transfer (ET), oxygen atom transfer (OAT), and hydrogen atom transfer (HAT) reactions. Herein, we report a contrasting effect of acids in the ET, OAT, and HAT reactions of a nickel(III) complex, [NiIII(PaPy3*)]2+ (1) in acetone/CH3CN (v/v 19:1). 1 was synthesized by reacting [NiII(PaPy3*)]+ (2) with magic blue or iodosylbenzene in the absence or presence of triflic acid (HOTf), respectively. Sulfoxidation of thioanisole by 1 and H2O occurred in the presence of HOTf, and the reaction rate increased proportionally with increasing concentration of HOTf ([HOTf]). The rate of ET from diacetylferrocene to 1 also increased linearly with increasing [HOTf]. In contrast, HAT from 9,10-dihydroanthracene (DHA) to 1 slowed down with increasing [HOTf], exhibiting an inversely proportional relation to [HOTf]. The accelerating effect of HOTf in the ET and OAT reactions was ascribed to the binding of H+ to the PaPy3* ligand of 2; the one-electron reduction potential (Ered) of 1 was positively shifted with increasing [HOTf]. Such a positive shift in the Ered value resulted in accelerating the ET and OAT reactions that proceeded via the rate-determining ET step. On the other hand, the decelerating effect of HOTf on HAT from DHA to 1 resulted from the inhibition of proton transfer from DHA•+ to 2 due to the binding of H+ to the PaPy3* ligand of 2. The ET reactions of 1 in the absence and presence of HOTf were well analyzed in light of the Marcus theory of ET in comparison with the HAT reactions.

中文翻译:

酸在镍 (III) 配合物的电子转移、氧原子转移和氢原子转移反应中的对比作用

酸在电子转移 (ET)、氧原子转移 (OAT) 和氢原子转移 (HAT) 反应中的加速作用有很多例子。在此,我们报告了酸在镍 (III) 络合物 [Ni III (PaPy 3 *)] 2+ ( 1 ) 在丙酮/CH 3 CN (v/v )的 ET、OAT 和 HAT 反应中的对比效果19:1)。1是通过 [Ni II (PaPy 3 *)] + ( 2 ) 在三氟甲磺酸 (HOTf) 存在或不存在下分别与魔幻蓝或碘代苯反应合成的。1和H 2磺化苯甲醚O 在 HOTf 存在的情况下发生,并且反应速率随着 HOTf ([HOTf]) 浓度的增加成比例增加。从二乙酰二茂铁到1的 ET 速率也随着 [HOTf] 的增加而线性增加。相反,从 9,10-二氢蒽 (DHA) 到1的 HAT随着 [HOTf] 的增加而减慢,与 [HOTf] 呈反比关系。HOTf 在 ET 和 OAT 反应中的加速作用归因于 H +与2的 PaPy 3 * 配体的结合;1的单电子还原电势 ( E red )随着 [HOTf] 的增加而正向移动。E红色的这种积极转变值导致加速通过决定速率的 ET 步骤进行的 ET 和 OAT 反应。另一方面,HOTf 对 HAT 从 DHA 到1的减速作用是由于 H +与2的 PaPy 3 * 配体结合而抑制质子从 DHA •+转移到2。与 HAT 反应相比,根据 ET 的 Marcus 理论,很好地分析了1在不存在和存在 HOTf 的情况下的 ET 反应。
更新日期:2022-11-29
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