Chen Zhou, Xi Zhang, Shan Zhao, Si-Dan Zhong, Xiao-Lv Ding, Shun-Ping Yang, Fuxing Pan*, Piao He and Xiao-Yi Yi*,
{"title":"含吡啶吡咯配体RuII（trpy）配合物催化选择性将氨转化为联氨","authors":"Chen Zhou, Xi Zhang, Shan Zhao, Si-Dan Zhong, Xiao-Lv Ding, Shun-Ping Yang, Fuxing Pan*, Piao He and Xiao-Yi Yi*, ","doi":"10.1021/acscatal.5c0011610.1021/acscatal.5c00116","DOIUrl":null,"url":null,"abstract":"<p >Interested by the rapid growth of Ru-based complexes as molecular ammonia oxidation catalysts, this article proposes a Ru<sup>II</sup>(trpy) complex bearing various pyridylpyrrole ligands as a model complex for the electrocatalytic oxidation of ammonia. Treatment of [Ru(trpy)(Cl)<sub>3</sub>] (trpy = 2,2′:6′,2″-terpyridine) with deprotonated 2,5-di(pyridin-2-yl)-1<i>H</i>-pyrrole (HL<sub>1</sub>), 6-(1<i>H</i>-pyrrol-2-yl)-2,2′-bipyridine (HL<sub>2</sub>), and 2-(3,4,5-trimethyl-1<i>H</i>-pyrrol-2-yl)pyridine (H<sub>2</sub>L<sub>3</sub>) ligands, followed by anionic metathesis of Cl<sup>–</sup> by PF<sub>6</sub><sup>–</sup>, affords [Ru(<i>K</i><sup>3</sup>-<i>N</i>,<i>N</i>′,<i>N</i>″-L<sub>1</sub>)(trpy)](PF<sub>6</sub>) (<b>Ru1</b>), [Ru(<i>K</i><sup>3</sup>-<i>N</i>,<i>N</i>′,<i>N</i>″-L<sub>2</sub>)(trpy)](PF<sub>6</sub>) (<b>Ru2</b>),and [Ru(<i>K</i><sup>3</sup>-<i>N</i>,<i>N</i>′,<i>N</i>″-L<sub>3</sub>)(trpy)] (<b>Ru3</b>), respectively. Ligad L<sub>1</sub><sup>–</sup> in <b>Ru1</b> is hemilabile and readily opens one armed-pyridine for incoming NH<sub>3</sub> coordination to generate [Ru(<i>K</i><sup>2</sup>-<i>N</i>,<i>N</i>′-L<sub>1</sub>)(trpy)(NH<sub>3</sub>)](PF<sub>6</sub>) (<b>Ru1-NH</b><sub><b>3</b></sub>). Unlike <b>Ru2</b> and <b>Ru3</b>, which are entirely devoid of catalysis for ammonia oxidation, complexes <b>Ru1</b> and <b>Ru1-NH</b><sub><b>3</b></sub> have highly selective electrocatalysis for the conversion of ammonia into hydrazine with 97.8% and 98.1% selectivity, respectively. The TOF<sub>max</sub> and Faradaic Efficiency (FE) of <b>Ru1</b> and <b>Ru1-NH</b><sub><b>3</b></sub> reach 316.4 h<sup>–1</sup> and 99.2% and 360.8 h<sup>–1</sup> and 99.1%, respectively. The cyclic voltammetric measurements combined with density functional theory (DFT) calculations illustrate that <b>Ru1-NH</b><sub><b>3</b></sub> undergoes the bimolecular coupling of Ru<sup>III</sup>-aminyl and Ru<sup>IV</sup>-iminyl to form N<sub>2</sub>H<sub>4</sub>. The foot of the wave analysis (FOWA) displays the corresponding apparent rate constant of 4.26 × 10<sup>6</sup> M<sup>–1</sup> s<sup>–1</sup>.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 4","pages":"3535–3545 3535–3545"},"PeriodicalIF":13.1000,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Catalytic Selective Conversion of Ammonia into Hydrazine by a RuII(trpy) Complex Bearing a Pyridylpyrrole Ligand\",\"authors\":\"Chen Zhou, Xi Zhang, Shan Zhao, Si-Dan Zhong, Xiao-Lv Ding, Shun-Ping Yang, Fuxing Pan*, Piao He and Xiao-Yi Yi*, \",\"doi\":\"10.1021/acscatal.5c0011610.1021/acscatal.5c00116\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Interested by the rapid growth of Ru-based complexes as molecular ammonia oxidation catalysts, this article proposes a Ru<sup>II</sup>(trpy) complex bearing various pyridylpyrrole ligands as a model complex for the electrocatalytic oxidation of ammonia. Treatment of [Ru(trpy)(Cl)<sub>3</sub>] (trpy = 2,2′:6′,2″-terpyridine) with deprotonated 2,5-di(pyridin-2-yl)-1<i>H</i>-pyrrole (HL<sub>1</sub>), 6-(1<i>H</i>-pyrrol-2-yl)-2,2′-bipyridine (HL<sub>2</sub>), and 2-(3,4,5-trimethyl-1<i>H</i>-pyrrol-2-yl)pyridine (H<sub>2</sub>L<sub>3</sub>) ligands, followed by anionic metathesis of Cl<sup>–</sup> by PF<sub>6</sub><sup>–</sup>, affords [Ru(<i>K</i><sup>3</sup>-<i>N</i>,<i>N</i>′,<i>N</i>″-L<sub>1</sub>)(trpy)](PF<sub>6</sub>) (<b>Ru1</b>), [Ru(<i>K</i><sup>3</sup>-<i>N</i>,<i>N</i>′,<i>N</i>″-L<sub>2</sub>)(trpy)](PF<sub>6</sub>) (<b>Ru2</b>),and [Ru(<i>K</i><sup>3</sup>-<i>N</i>,<i>N</i>′,<i>N</i>″-L<sub>3</sub>)(trpy)] (<b>Ru3</b>), respectively. Ligad L<sub>1</sub><sup>–</sup> in <b>Ru1</b> is hemilabile and readily opens one armed-pyridine for incoming NH<sub>3</sub> coordination to generate [Ru(<i>K</i><sup>2</sup>-<i>N</i>,<i>N</i>′-L<sub>1</sub>)(trpy)(NH<sub>3</sub>)](PF<sub>6</sub>) (<b>Ru1-NH</b><sub><b>3</b></sub>). Unlike <b>Ru2</b> and <b>Ru3</b>, which are entirely devoid of catalysis for ammonia oxidation, complexes <b>Ru1</b> and <b>Ru1-NH</b><sub><b>3</b></sub> have highly selective electrocatalysis for the conversion of ammonia into hydrazine with 97.8% and 98.1% selectivity, respectively. The TOF<sub>max</sub> and Faradaic Efficiency (FE) of <b>Ru1</b> and <b>Ru1-NH</b><sub><b>3</b></sub> reach 316.4 h<sup>–1</sup> and 99.2% and 360.8 h<sup>–1</sup> and 99.1%, respectively. The cyclic voltammetric measurements combined with density functional theory (DFT) calculations illustrate that <b>Ru1-NH</b><sub><b>3</b></sub> undergoes the bimolecular coupling of Ru<sup>III</sup>-aminyl and Ru<sup>IV</sup>-iminyl to form N<sub>2</sub>H<sub>4</sub>. The foot of the wave analysis (FOWA) displays the corresponding apparent rate constant of 4.26 × 10<sup>6</sup> M<sup>–1</sup> s<sup>–1</sup>.</p>\",\"PeriodicalId\":9,\"journal\":{\"name\":\"ACS Catalysis \",\"volume\":\"15 4\",\"pages\":\"3535–3545 3535–3545\"},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2025-02-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Catalysis \",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acscatal.5c00116\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acscatal.5c00116","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Catalytic Selective Conversion of Ammonia into Hydrazine by a RuII(trpy) Complex Bearing a Pyridylpyrrole Ligand
Interested by the rapid growth of Ru-based complexes as molecular ammonia oxidation catalysts, this article proposes a RuII(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 TOFmax 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 RuIII-aminyl and RuIV-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.
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.
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