Effect of Ligand Backbone on the Electrochemical Hydrogen Evolution Reaction and Hydrogen-Atom-Transfer Reactivity Using a Nickel Polypyridine Quinoline Complex

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Pub Date : 2025-04-16 DOI:10.1021/acs.inorgchem.4c05512

Sabarni Paul, Subhankar Sutradhar, Aniruddha Paik, Amit Biswas, Soumadip Das, Chandan Das, Rajib Maity, Alok Mahata, Siba P. Midya, Bholanath Maity, Sujoy Rana

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Abstract

Redox-active quinoline-containing [Ni^II(2PyN2Q) (H₂O)]²⁺ complex (1) has been developed for the electrocatalytic (e) hydrogen evolution reaction (HER) in the presence of organic acids and water and for the hydrogen-atom-transfer (HAT) reaction with styrene in the presence of acids. Complex 1 shows promising e-HER performance in water up to pH 9. It exhibits a stepwise (E)ECEC mechanism with AcOH, while a potential-dependent bimolecular homolytic pathway and CEEC mechanism is operative with p-toluene sulfonic acid during the e-HER. The one- and two-electron-reduced species of 1 are characterized by spectro-electrochemistry, optical, and EPR studies. Moreover, the inverse kinetic isotope effect (KIE = 0.83) between AcOH and d₄-AcOH during the e-HER and e-HAT with styrene for the hydro-functionalization reaction using catalyst 1 possibly suggests the involvement of nickel hydride species. The e-HER and e-HAT reactivity of 1 have been compared with redox-inactive redox-inactive [Ni^II(N4Py)(H₂O)]²⁺ (2), demonstrating the prominent effect of quinoline in the e-HER and pyridine in the e-HAT. The proposed mechanism of the e-HER with AcOH is well supported by DFT studies.

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配体骨架对镍-多吡啶-喹啉配合物电化学析氢反应和氢原子转移反应活性的影响

研究了含氧化还原活性喹啉的[NiII(2PyN2Q) (H2O)]2+配合物(1)，用于有机酸和水存在下的电催化(e)析氢反应（HER）和酸存在下与苯乙烯的氢原子转移（HAT）反应。配合物1在pH达9的水中表现出良好的e-HER性能。在与AcOH的E - her反应中，其表现为一种阶梯(E)ECEC机制，而在与对甲苯磺酸的E - her反应中，其表现为一种电位依赖的双分子均溶途径和CEEC机制。1的一电子和二电子还原态通过光谱电化学、光学和EPR研究进行了表征。此外，在催化剂1与苯乙烯的e-HER和e-HAT加氢官能化反应中，AcOH和d4-AcOH之间的逆动力学同位素效应（KIE = 0.83）表明可能有氢化镍的参与。将1的e-HER和e-HAT的反应活性与无氧化还原活性的[NiII(N4Py)(H2O)]2+(2)进行了比较，表明喹啉在e-HER中的作用突出，吡啶在e-HAT中的作用突出。DFT研究很好地支持了AcOH与e-HER的作用机制。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.