Joshua Parche, Robin Sievers, Tim-Niclas Streit, Moritz Malischewski
{"title":"锇(VI)氮配合物与全氟醇配体:通过简单的氧化银介导的合成路线扩大配体范围","authors":"Joshua Parche, Robin Sievers, Tim-Niclas Streit, Moritz Malischewski","doi":"10.1002/ejic.202500335","DOIUrl":null,"url":null,"abstract":"<p>The coordination of perfluorinated alcohols toward an osmium(VI) nitrido center is described. Herein, [NBu<sub>4</sub>][OsNCl<sub>4</sub>] is reacted with hexafluoroacetone hydrate (HFA), perfluoropinacol (PFP), or pentafluorophenol (C<sub>6</sub>F<sub>5</sub>OH) in the presence of Ag<sub>2</sub>O to obtain the stable complexes [NBu<sub>4</sub>][Os(N)(O<sub>2</sub>C(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub>] (<b>1</b>), [NBu<sub>4</sub>][Os(N)(O<sub>2</sub>C<sub>2</sub>(CF<sub>3</sub>)<sub>4</sub>)<sub>2</sub>] (<b>2</b>), [NBu<sub>4</sub>][Os(N)(OC<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (<b>3</b>), and [NBu<sub>4</sub>][Os(N)(Cl)<sub>2</sub>(O<sub>2</sub>C(CF<sub>3</sub>)<sub>2</sub>)] (<b>4</b>) in overall good yields. These complexes represent rare examples of Os(VI) nitrido complexes that carry four <i>O</i>-donor ligands, as no examples have been reported for perfluorinated alcoholates so far. Complexes <b>1</b> and <b>4</b> extend the coordination chemistry of the otherwise underrepresented O<sub>2</sub>C(CF<sub>3</sub>)<sub>2</sub> ligand. The latter offers the potential for further functionalization of the osmium(VI) nitrido complex through substitution of the remaining chloride ligands. The compounds are fully characterized, and the crystal structures of compounds <b>1</b>, <b>2,</b> and <b>3</b> are analyzed.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 26","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500335","citationCount":"0","resultStr":"{\"title\":\"Osmium(VI) Nitrido Complexes with Perfluorinated Alcoholate Ligands: Expanding Ligand Scope through a Simple Silver Oxide-Mediated Synthesis Route\",\"authors\":\"Joshua Parche, Robin Sievers, Tim-Niclas Streit, Moritz Malischewski\",\"doi\":\"10.1002/ejic.202500335\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The coordination of perfluorinated alcohols toward an osmium(VI) nitrido center is described. Herein, [NBu<sub>4</sub>][OsNCl<sub>4</sub>] is reacted with hexafluoroacetone hydrate (HFA), perfluoropinacol (PFP), or pentafluorophenol (C<sub>6</sub>F<sub>5</sub>OH) in the presence of Ag<sub>2</sub>O to obtain the stable complexes [NBu<sub>4</sub>][Os(N)(O<sub>2</sub>C(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub>] (<b>1</b>), [NBu<sub>4</sub>][Os(N)(O<sub>2</sub>C<sub>2</sub>(CF<sub>3</sub>)<sub>4</sub>)<sub>2</sub>] (<b>2</b>), [NBu<sub>4</sub>][Os(N)(OC<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (<b>3</b>), and [NBu<sub>4</sub>][Os(N)(Cl)<sub>2</sub>(O<sub>2</sub>C(CF<sub>3</sub>)<sub>2</sub>)] (<b>4</b>) in overall good yields. These complexes represent rare examples of Os(VI) nitrido complexes that carry four <i>O</i>-donor ligands, as no examples have been reported for perfluorinated alcoholates so far. Complexes <b>1</b> and <b>4</b> extend the coordination chemistry of the otherwise underrepresented O<sub>2</sub>C(CF<sub>3</sub>)<sub>2</sub> ligand. The latter offers the potential for further functionalization of the osmium(VI) nitrido complex through substitution of the remaining chloride ligands. The compounds are fully characterized, and the crystal structures of compounds <b>1</b>, <b>2,</b> and <b>3</b> are analyzed.</p>\",\"PeriodicalId\":38,\"journal\":{\"name\":\"European Journal of Inorganic Chemistry\",\"volume\":\"28 26\",\"pages\":\"\"},\"PeriodicalIF\":2.0000,\"publicationDate\":\"2025-08-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500335\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"European Journal of Inorganic Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202500335\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Journal of Inorganic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202500335","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Osmium(VI) Nitrido Complexes with Perfluorinated Alcoholate Ligands: Expanding Ligand Scope through a Simple Silver Oxide-Mediated Synthesis Route
The coordination of perfluorinated alcohols toward an osmium(VI) nitrido center is described. Herein, [NBu4][OsNCl4] is reacted with hexafluoroacetone hydrate (HFA), perfluoropinacol (PFP), or pentafluorophenol (C6F5OH) in the presence of Ag2O to obtain the stable complexes [NBu4][Os(N)(O2C(CF3)2)2] (1), [NBu4][Os(N)(O2C2(CF3)4)2] (2), [NBu4][Os(N)(OC6F5)4] (3), and [NBu4][Os(N)(Cl)2(O2C(CF3)2)] (4) in overall good yields. These complexes represent rare examples of Os(VI) nitrido complexes that carry four O-donor ligands, as no examples have been reported for perfluorinated alcoholates so far. Complexes 1 and 4 extend the coordination chemistry of the otherwise underrepresented O2C(CF3)2 ligand. The latter offers the potential for further functionalization of the osmium(VI) nitrido complex through substitution of the remaining chloride ligands. The compounds are fully characterized, and the crystal structures of compounds 1, 2, and 3 are analyzed.
期刊介绍:
The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry:
Chemische Berichte
Bulletin des Sociétés Chimiques Belges
Bulletin de la Société Chimique de France
Gazzetta Chimica Italiana
Recueil des Travaux Chimiques des Pays-Bas
Anales de Química
Chimika Chronika
Revista Portuguesa de Química
ACH—Models in Chemistry
Polish Journal of Chemistry
The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.