{"title":"含 N,N-二乙基二硫代氨基甲酸酯和取代膦的氟硫酸盐锇(III)和锇(IV)配合物：合成、晶体结构和 DFT 研究","authors":"Bertín Anzaldo, Andrés Álvarez-García, Sylvain Bernès, Armando Ramírez-Monroy, Maribel Arroyo-Carranza","doi":"10.1002/hlca.202400066","DOIUrl":null,"url":null,"abstract":"<p>The paramagnetic osmium(III) [Os(SR<sub>F</sub>)(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub>(P(C<sub>6</sub>H<sub>4</sub>X-4)<sub>3</sub>)] (R<sub>F</sub>=C<sub>6</sub>F<sub>4</sub>H−4, C<sub>6</sub>F<sub>5</sub>; X=OCH<sub>3</sub>, CH<sub>3</sub>, F) (<b>1–6</b>) along with diamagnetic osmium(IV) [Os(SR<sub>F</sub>)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub>] (<b>7–8</b>) complexes were obtained from [Os(SR<sub>F</sub>)<sub>4</sub>(P(C<sub>6</sub>H<sub>4</sub>-X)<sub>3</sub>)] and NaS<sub>2</sub>CNEt<sub>2</sub>, which were characterized by FAB mass spectrometry, IR spectroscopy, single crystal X-ray diffraction, and for the diamagnetic <b>7</b> also by NMR. TD-DFT calculations were performed to simulate the absorption spectra of complexes. In the visible region, LMCT transitions contribute to the calculated intensities, which are somewhat related to the color of the synthesized compounds. In the ultraviolet region, the phosphine ligand plays a significant role in MLCT transitions, which results in Os(III) complexes exhibiting an intense band in that region. Topological analysis and electron localization function (ELF) maps calculated for <b>6</b> and <b>7</b> confirm the strong ionic character of the Os−S coordination bonds formed by the thiophenolate and dithiocarbamate ligands. This comprehensive study provides information on the structure, bonding, and electronic properties of osmium complexes, for potential applications in catalysis, materials science, and biological systems.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Fluorinated-Thiolate Osmium(III) and Osmium(IV) Complexes Bearing N,N-diethyldithiocarbamate and Substituted Phosphines. Synthesis, Crystal Structures and DFT-Studies\",\"authors\":\"Bertín Anzaldo, Andrés Álvarez-García, Sylvain Bernès, Armando Ramírez-Monroy, Maribel Arroyo-Carranza\",\"doi\":\"10.1002/hlca.202400066\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The paramagnetic osmium(III) [Os(SR<sub>F</sub>)(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub>(P(C<sub>6</sub>H<sub>4</sub>X-4)<sub>3</sub>)] (R<sub>F</sub>=C<sub>6</sub>F<sub>4</sub>H−4, C<sub>6</sub>F<sub>5</sub>; X=OCH<sub>3</sub>, CH<sub>3</sub>, F) (<b>1–6</b>) along with diamagnetic osmium(IV) [Os(SR<sub>F</sub>)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub>] (<b>7–8</b>) complexes were obtained from [Os(SR<sub>F</sub>)<sub>4</sub>(P(C<sub>6</sub>H<sub>4</sub>-X)<sub>3</sub>)] and NaS<sub>2</sub>CNEt<sub>2</sub>, which were characterized by FAB mass spectrometry, IR spectroscopy, single crystal X-ray diffraction, and for the diamagnetic <b>7</b> also by NMR. TD-DFT calculations were performed to simulate the absorption spectra of complexes. In the visible region, LMCT transitions contribute to the calculated intensities, which are somewhat related to the color of the synthesized compounds. In the ultraviolet region, the phosphine ligand plays a significant role in MLCT transitions, which results in Os(III) complexes exhibiting an intense band in that region. Topological analysis and electron localization function (ELF) maps calculated for <b>6</b> and <b>7</b> confirm the strong ionic character of the Os−S coordination bonds formed by the thiophenolate and dithiocarbamate ligands. This comprehensive study provides information on the structure, bonding, and electronic properties of osmium complexes, for potential applications in catalysis, materials science, and biological systems.</p>\",\"PeriodicalId\":1,\"journal\":{\"name\":\"Accounts of Chemical Research\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.4000,\"publicationDate\":\"2024-07-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Accounts of Chemical Research\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400066\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Accounts of Chemical Research","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400066","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Fluorinated-Thiolate Osmium(III) and Osmium(IV) Complexes Bearing N,N-diethyldithiocarbamate and Substituted Phosphines. Synthesis, Crystal Structures and DFT-Studies
The paramagnetic osmium(III) [Os(SRF)(S2CNEt2)2(P(C6H4X-4)3)] (RF=C6F4H−4, C6F5; X=OCH3, CH3, F) (1–6) along with diamagnetic osmium(IV) [Os(SRF)2(S2CNEt2)2] (7–8) complexes were obtained from [Os(SRF)4(P(C6H4-X)3)] and NaS2CNEt2, which were characterized by FAB mass spectrometry, IR spectroscopy, single crystal X-ray diffraction, and for the diamagnetic 7 also by NMR. TD-DFT calculations were performed to simulate the absorption spectra of complexes. In the visible region, LMCT transitions contribute to the calculated intensities, which are somewhat related to the color of the synthesized compounds. In the ultraviolet region, the phosphine ligand plays a significant role in MLCT transitions, which results in Os(III) complexes exhibiting an intense band in that region. Topological analysis and electron localization function (ELF) maps calculated for 6 and 7 confirm the strong ionic character of the Os−S coordination bonds formed by the thiophenolate and dithiocarbamate ligands. This comprehensive study provides information on the structure, bonding, and electronic properties of osmium complexes, for potential applications in catalysis, materials science, and biological systems.
期刊介绍：
Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance.
Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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