Binglin Lei, Fanshu Cao, Ming Chen, Xuyang Wang and Zhenbo Mo*,
{"title":"Bisgermylene-Stabilized Stannylone: Catalytic Reduction of Nitrous Oxide and Nitro Compounds via Element-Ligand Cooperativity","authors":"Binglin Lei, Fanshu Cao, Ming Chen, Xuyang Wang and Zhenbo Mo*, ","doi":"10.1021/jacs.4c03227","DOIUrl":null,"url":null,"abstract":"<p >This study describes the synthesis, structural characterization, and catalytic application of a bis(germylene)-stabilized stannylone (<b>2</b>). The reduction of digermylated stannylene (<b>1</b>) with 2.2 equiv of potassium graphite (KC<sub>8</sub>) leads to the formation of stannylone <b>2</b> as a green solid in 78% yield. Computational studies showed that stannylone <b>2</b> possesses a formal Sn(0) center and a delocalized 3-c-2-e π-bond in the Ge<sub>2</sub>Sn core, which arises from back-donation of the p-type lone pair electrons on the Sn atom to the vacant orbitals of the Ge atoms. Stannylone <b>2</b> can serve as an efficient precatalyst for the selective reduction of nitrous oxide (N<sub>2</sub>O) and nitroarenes (ArNO<sub>2</sub>) with the formation of dinitrogen (N<sub>2</sub>) and hydrazines (ArNH–NHAr), respectively. Exposure of <b>2</b> with N<sub>2</sub>O (1 atm) resulted in the insertion of two oxygen atoms into the Ge–Ge and Ge–Sn bonds, yielding the germyl(oxyl)stannylene (<b>3</b>). Moreover, the stoichiometric reaction of <b>2</b> with 1-chloro-4-nitrobenzene afforded an amido(oxyl)stannylene (<b>4</b>) through the complete scission of the N–O bonds of the nitroarene. Stannylenes <b>3</b> and <b>4</b> serve as catalytically active species for the catalytic reduction of nitrous oxide and nitroarenes, respectively. Mechanistic studies reveal that the cooperation of the low-valent Ge and Sn centers allows for multiple electron transfers to cleave the N–O bonds of N<sub>2</sub>O and ArNO<sub>2</sub>. This approach presents a new strategy for catalyzing the deoxygenation of N<sub>2</sub>O and ArNO<sub>2</sub> using a zerovalent tin compound.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c03227","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
This study describes the synthesis, structural characterization, and catalytic application of a bis(germylene)-stabilized stannylone (2). The reduction of digermylated stannylene (1) with 2.2 equiv of potassium graphite (KC8) leads to the formation of stannylone 2 as a green solid in 78% yield. Computational studies showed that stannylone 2 possesses a formal Sn(0) center and a delocalized 3-c-2-e π-bond in the Ge2Sn core, which arises from back-donation of the p-type lone pair electrons on the Sn atom to the vacant orbitals of the Ge atoms. Stannylone 2 can serve as an efficient precatalyst for the selective reduction of nitrous oxide (N2O) and nitroarenes (ArNO2) with the formation of dinitrogen (N2) and hydrazines (ArNH–NHAr), respectively. Exposure of 2 with N2O (1 atm) resulted in the insertion of two oxygen atoms into the Ge–Ge and Ge–Sn bonds, yielding the germyl(oxyl)stannylene (3). Moreover, the stoichiometric reaction of 2 with 1-chloro-4-nitrobenzene afforded an amido(oxyl)stannylene (4) through the complete scission of the N–O bonds of the nitroarene. Stannylenes 3 and 4 serve as catalytically active species for the catalytic reduction of nitrous oxide and nitroarenes, respectively. Mechanistic studies reveal that the cooperation of the low-valent Ge and Sn centers allows for multiple electron transfers to cleave the N–O bonds of N2O and ArNO2. This approach presents a new strategy for catalyzing the deoxygenation of N2O and ArNO2 using a zerovalent tin compound.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.