Madeleine C. Uible, Brandon S. Prokop, Daniel C. Hayes, Subhajyoti Chaudhuri, Kiruba Catherine Vincent, Apurva A. Pradhan, Ace Rounds, Jonathan W. Turnley, Shubhanshu Agarwal, Ryan N. Swope, George C. Schatz, Rakesh Agrawal, Suzanne C. Bart
{"title":"通过插入 CS2 生成同色锆和铪二硫代氨基甲酸酯：断键和命名","authors":"Madeleine C. Uible, Brandon S. Prokop, Daniel C. Hayes, Subhajyoti Chaudhuri, Kiruba Catherine Vincent, Apurva A. Pradhan, Ace Rounds, Jonathan W. Turnley, Shubhanshu Agarwal, Ryan N. Swope, George C. Schatz, Rakesh Agrawal, Suzanne C. Bart","doi":"10.1021/acs.organomet.4c00152","DOIUrl":null,"url":null,"abstract":"Syntheses of homoleptic zirconium and hafnium dithiocarbamates via carbon disulfide insertion into zirconium and hafnium amides were investigated for their utility as soluble molecular precursors for chalcogenide perovskites and binary metal sulfides. Treating M(NEtR)<sub>4</sub> (M = Zr, Hf and R = Me, Et) with CS<sub>2</sub> resulted in quantitative yields of homoleptic Group IV dithiocarbamates. Zr(κ<sup>2</sup>-S<sub>2</sub>CNMeEt) (<b>1</b>), Zr(κ<sup>2</sup>-S<sub>2</sub>CNEt<sub>2</sub>)<sub>4</sub> (<b>2</b>), and Hf(κ<sup>2</sup>-S<sub>2</sub>CNEt<sub>2</sub>)<sub>4</sub> (<b>4</b>), a rare example of a crystal of a homoleptic hafnium CS<sub>2</sub>-inserted amide species, were characterized. Computational analysis confirmed the assignments for IR spectroscopy. To exemplify the utility of the Group IV dithiocarbamates, a solution-phase nanoparticle synthesis was performed to obtain ZrS<sub>3</sub> via the thermal decomposition of Zr(S<sub>2</sub>CNMeEt)<sub>4</sub>.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Formation of Homoleptic Zirconium and Hafnium Dithiocarbamates via Insertion of CS2: Breaking Bonds and Taking Names\",\"authors\":\"Madeleine C. Uible, Brandon S. Prokop, Daniel C. Hayes, Subhajyoti Chaudhuri, Kiruba Catherine Vincent, Apurva A. Pradhan, Ace Rounds, Jonathan W. Turnley, Shubhanshu Agarwal, Ryan N. Swope, George C. Schatz, Rakesh Agrawal, Suzanne C. Bart\",\"doi\":\"10.1021/acs.organomet.4c00152\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Syntheses of homoleptic zirconium and hafnium dithiocarbamates via carbon disulfide insertion into zirconium and hafnium amides were investigated for their utility as soluble molecular precursors for chalcogenide perovskites and binary metal sulfides. Treating M(NEtR)<sub>4</sub> (M = Zr, Hf and R = Me, Et) with CS<sub>2</sub> resulted in quantitative yields of homoleptic Group IV dithiocarbamates. Zr(κ<sup>2</sup>-S<sub>2</sub>CNMeEt) (<b>1</b>), Zr(κ<sup>2</sup>-S<sub>2</sub>CNEt<sub>2</sub>)<sub>4</sub> (<b>2</b>), and Hf(κ<sup>2</sup>-S<sub>2</sub>CNEt<sub>2</sub>)<sub>4</sub> (<b>4</b>), a rare example of a crystal of a homoleptic hafnium CS<sub>2</sub>-inserted amide species, were characterized. Computational analysis confirmed the assignments for IR spectroscopy. To exemplify the utility of the Group IV dithiocarbamates, a solution-phase nanoparticle synthesis was performed to obtain ZrS<sub>3</sub> via the thermal decomposition of Zr(S<sub>2</sub>CNMeEt)<sub>4</sub>.\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-06-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00152\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00152","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Formation of Homoleptic Zirconium and Hafnium Dithiocarbamates via Insertion of CS2: Breaking Bonds and Taking Names
Syntheses of homoleptic zirconium and hafnium dithiocarbamates via carbon disulfide insertion into zirconium and hafnium amides were investigated for their utility as soluble molecular precursors for chalcogenide perovskites and binary metal sulfides. Treating M(NEtR)4 (M = Zr, Hf and R = Me, Et) with CS2 resulted in quantitative yields of homoleptic Group IV dithiocarbamates. Zr(κ2-S2CNMeEt) (1), Zr(κ2-S2CNEt2)4 (2), and Hf(κ2-S2CNEt2)4 (4), a rare example of a crystal of a homoleptic hafnium CS2-inserted amide species, were characterized. Computational analysis confirmed the assignments for IR spectroscopy. To exemplify the utility of the Group IV dithiocarbamates, a solution-phase nanoparticle synthesis was performed to obtain ZrS3 via the thermal decomposition of Zr(S2CNMeEt)4.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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