Osmium(VI) Nitrido Complexes with Perfluorinated Alcoholate Ligands: Expanding Ligand Scope through a Simple Silver Oxide-Mediated Synthesis Route

IF 2 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry Pub Date : 2025-08-20 DOI:10.1002/ejic.202500335

Joshua Parche, Robin Sievers, Tim-Niclas Streit, Moritz Malischewski

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Abstract

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.

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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

描述了全氟醇对锇（VI）腈中心的配位。在此，[NBu4][OsNCl4]与六氟丙酮水合物（HFA）、全氟opinacol （PFP）或五氟苯酚（C6F5OH）在Ag2O存在下反应，得到稳定的配合物[NBu4][Os(N)(O2C(CF3)2)2](1)、[NBu4][Os(N)(O2C2(CF3)4)2](2)、[NBu4][Os(N)(OC6F5)4](3)和[NBu4][Os(N)(O2C(CF3)2)](4)，总体产率较高。这些配合物是携带四个o给体配体的o （VI）硝基络合物的罕见例子，因为迄今为止还没有报道过全氟醇的例子。配合物1和4扩展了O2C(CF3)2配体的配位化学。后者提供了通过取代剩余的氯配体进一步功能化氮化锇配合物的潜力。对化合物进行了全面表征，并对化合物1、2和3的晶体结构进行了分析。

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来源期刊

European Journal of Inorganic Chemistry 化学-无机化学与核化学

CiteScore

4.30

自引率

4.30%

发文量

419

审稿时长

1.3 months

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.