Catalytic Selective Conversion of Ammonia into Hydrazine by a RuII(trpy) Complex Bearing a Pyridylpyrrole Ligand

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-02-12 DOI:10.1021/acscatal.5c0011610.1021/acscatal.5c00116

Chen Zhou, Xi Zhang, Shan Zhao, Si-Dan Zhong, Xiao-Lv Ding, Shun-Ping Yang, Fuxing Pan*, Piao He and Xiao-Yi Yi*,

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Abstract

Interested by the rapid growth of Ru-based complexes as molecular ammonia oxidation catalysts, this article proposes a Ru^II(trpy) complex bearing various pyridylpyrrole ligands as a model complex for the electrocatalytic oxidation of ammonia. Treatment of [Ru(trpy)(Cl)₃] (trpy = 2,2′:6′,2″-terpyridine) with deprotonated 2,5-di(pyridin-2-yl)-1H-pyrrole (HL₁), 6-(1H-pyrrol-2-yl)-2,2′-bipyridine (HL₂), and 2-(3,4,5-trimethyl-1H-pyrrol-2-yl)pyridine (H₂L₃) ligands, followed by anionic metathesis of Cl^– by PF₆^–, affords [Ru(K³-N,N′,N″-L₁)(trpy)](PF₆) (Ru1), [Ru(K³-N,N′,N″-L₂)(trpy)](PF₆) (Ru2),and [Ru(K³-N,N′,N″-L₃)(trpy)] (Ru3), respectively. Ligad L₁^– in Ru1 is hemilabile and readily opens one armed-pyridine for incoming NH₃ coordination to generate [Ru(K²-N,N′-L₁)(trpy)(NH₃)](PF₆) (Ru1-NH₃). Unlike Ru2 and Ru3, which are entirely devoid of catalysis for ammonia oxidation, complexes Ru1 and Ru1-NH₃ have highly selective electrocatalysis for the conversion of ammonia into hydrazine with 97.8% and 98.1% selectivity, respectively. The TOF_max and Faradaic Efficiency (FE) of Ru1 and Ru1-NH₃ reach 316.4 h^–1 and 99.2% and 360.8 h^–1 and 99.1%, respectively. The cyclic voltammetric measurements combined with density functional theory (DFT) calculations illustrate that Ru1-NH₃ undergoes the bimolecular coupling of Ru^III-aminyl and Ru^IV-iminyl to form N₂H₄. The foot of the wave analysis (FOWA) displays the corresponding apparent rate constant of 4.26 × 10⁶ M^–1 s^–1.

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含吡啶吡咯配体RuII（trpy）配合物催化选择性将氨转化为联氨

由于ru基配合物作为氨氧化分子催化剂的快速发展，本文提出了一种含有多种吡啶吡咯配体的RuII（trpy）配合物作为氨电催化氧化的模型配合物。用去质子化的2,5-二（吡啶-2-基）- 1h -吡啶（HL1）、6-（1h -吡啶-2-基）-2,2 ' -联吡啶（HL2）和2-（3,4,5-三甲基- 1h -吡啶-2-基）吡啶（H2L3）配体处理[Ru(trpy)(trpy) 3] (trpy))(PF6 -)（Ru1）、[Ru(K3-N,N ',N″- l2)(trpy)](PF6) （Ru2）和[Ru(K3-N,N ',N″- l3)(trpy)]（Ru3）。Ru1中的Ligad L1 -是半可溶的，容易打开单臂吡啶，使进入的NH3配位生成[Ru(K2-N,N ' -L1)(trpy)(NH3)](PF6) （Ru1-NH3）。与Ru2和Ru3完全没有氨氧化催化作用不同，配合物Ru1和Ru1- nh3对氨转化为联氨具有高选择性电催化作用，选择性分别为97.8%和98.1%。Ru1和Ru1- nh3的TOFmax和Faradaic Efficiency （FE）分别达到316.4 h-1和99.2%和360.8 h-1和99.1%。循环伏安测量结合密度泛函理论（DFT）计算表明，Ru1-NH3经历了ruiii -胺基和ruiv -亚胺基的双分子偶联形成N2H4。波脚分析（FOWA）显示相应的表观速率常数为4.26 × 106 M-1 s-1。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.