Domenik Nowak, Guilhem Claude, Anna-Maria Tsirigoni, Adelheid Hagenbach, Joshua S. Figueroa* and Ulrich Abram*,
{"title":"空间负载间terphenyl异氰酸酯与锝、铼的硫代硝基配合物─空间块体物质","authors":"Domenik Nowak, Guilhem Claude, Anna-Maria Tsirigoni, Adelheid Hagenbach, Joshua S. Figueroa* and Ulrich Abram*, ","doi":"10.1021/acs.organomet.5c00250","DOIUrl":null,"url":null,"abstract":"<p >Low-valent thionitrosyl complexes of technetium and rhenium with the bulky isocyanides CNAr<sup>Tripp2</sup>, CNAr<sup>Dipp2</sup>, and CNAr<sup>Mes2</sup> (Tripp = 2,4,6-triisopropylphenyl, Dipp = 2,6-diisopropylphenyl, Mes = 2,4,6-trimethylphenyl) have been synthesized by reactions of the corresponding nitridotechnetium(V) or rhenium(V) compounds with disulfur dichloride. The structures of the products and the oxidation states of the resulting metal ions are mainly controlled by the steric bulk of the terphenyl isocyanide ligands. Bis(isocyanide) Tc(II) and Re(II) were obtained exclusively with CNAr<sup>Tripp2</sup> or CNAr<sup>Dipp2</sup>, which is in contrast with the more diverse reaction outcomes with the less bulky CNAr<sup>Mes2</sup>, where the products also include metal(I) and dimeric compounds. The obtained complexes [Re<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>(MeOH)], [Re<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Dipp2</sup>)<sub>2</sub>], [Re<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Mes2</sup>)<sub>3</sub>], [Tc<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>], [Re<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>], [Re<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Dipp2</sup>)<sub>2</sub>], [Re<sup>I</sup>(NS)Cl<sub>2</sub>(CNAr<sup>Mes2</sup>)<sub>3</sub>], [Tc<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>], [Tc<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Dipp2</sup>)<sub>2</sub>], [Tc<sup>II</sup>(NS)Cl<sub>2</sub>(CNAr<sup>Mes2</sup>)<sub>3</sub>]Cl, and [{Tc(NS)Cl(CNAr<sup>Mes2</sup>)<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub>] were studied spectroscopically and partially by X-ray diffraction.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1965–1976"},"PeriodicalIF":2.9000,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00250","citationCount":"0","resultStr":"{\"title\":\"Thionitrosyl Complexes of Technetium and Rhenium with Sterically Encumbered m-Terphenyl Isocyanides─Steric Bulk Matters\",\"authors\":\"Domenik Nowak, Guilhem Claude, Anna-Maria Tsirigoni, Adelheid Hagenbach, Joshua S. Figueroa* and Ulrich Abram*, \",\"doi\":\"10.1021/acs.organomet.5c00250\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Low-valent thionitrosyl complexes of technetium and rhenium with the bulky isocyanides CNAr<sup>Tripp2</sup>, CNAr<sup>Dipp2</sup>, and CNAr<sup>Mes2</sup> (Tripp = 2,4,6-triisopropylphenyl, Dipp = 2,6-diisopropylphenyl, Mes = 2,4,6-trimethylphenyl) have been synthesized by reactions of the corresponding nitridotechnetium(V) or rhenium(V) compounds with disulfur dichloride. The structures of the products and the oxidation states of the resulting metal ions are mainly controlled by the steric bulk of the terphenyl isocyanide ligands. Bis(isocyanide) Tc(II) and Re(II) were obtained exclusively with CNAr<sup>Tripp2</sup> or CNAr<sup>Dipp2</sup>, which is in contrast with the more diverse reaction outcomes with the less bulky CNAr<sup>Mes2</sup>, where the products also include metal(I) and dimeric compounds. The obtained complexes [Re<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>(MeOH)], [Re<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Dipp2</sup>)<sub>2</sub>], [Re<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Mes2</sup>)<sub>3</sub>], [Tc<sup>V</sup>NCl<sub>2</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>], [Re<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>], [Re<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Dipp2</sup>)<sub>2</sub>], [Re<sup>I</sup>(NS)Cl<sub>2</sub>(CNAr<sup>Mes2</sup>)<sub>3</sub>], [Tc<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Tripp2</sup>)<sub>2</sub>], [Tc<sup>II</sup>(NS)Cl<sub>3</sub>(CNAr<sup>Dipp2</sup>)<sub>2</sub>], [Tc<sup>II</sup>(NS)Cl<sub>2</sub>(CNAr<sup>Mes2</sup>)<sub>3</sub>]Cl, and [{Tc(NS)Cl(CNAr<sup>Mes2</sup>)<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub>] were studied spectroscopically and partially by X-ray diffraction.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"44 17\",\"pages\":\"1965–1976\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-08-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00250\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00250\",\"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://pubs.acs.org/doi/10.1021/acs.organomet.5c00250","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Thionitrosyl Complexes of Technetium and Rhenium with Sterically Encumbered m-Terphenyl Isocyanides─Steric Bulk Matters
Low-valent thionitrosyl complexes of technetium and rhenium with the bulky isocyanides CNArTripp2, CNArDipp2, and CNArMes2 (Tripp = 2,4,6-triisopropylphenyl, Dipp = 2,6-diisopropylphenyl, Mes = 2,4,6-trimethylphenyl) have been synthesized by reactions of the corresponding nitridotechnetium(V) or rhenium(V) compounds with disulfur dichloride. The structures of the products and the oxidation states of the resulting metal ions are mainly controlled by the steric bulk of the terphenyl isocyanide ligands. Bis(isocyanide) Tc(II) and Re(II) were obtained exclusively with CNArTripp2 or CNArDipp2, which is in contrast with the more diverse reaction outcomes with the less bulky CNArMes2, where the products also include metal(I) and dimeric compounds. The obtained complexes [ReVNCl2(CNArTripp2)2(MeOH)], [ReVNCl2(CNArDipp2)2], [ReVNCl2(CNArMes2)3], [TcVNCl2(CNArTripp2)2], [ReII(NS)Cl3(CNArTripp2)2], [ReII(NS)Cl3(CNArDipp2)2], [ReI(NS)Cl2(CNArMes2)3], [TcII(NS)Cl3(CNArTripp2)2], [TcII(NS)Cl3(CNArDipp2)2], [TcII(NS)Cl2(CNArMes2)3]Cl, and [{Tc(NS)Cl(CNArMes2)2}2Cl2] were studied spectroscopically and partially by X-ray diffraction.
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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