Joy Mukhopadhyay, Prasad V. Bharatam, Subash Chandra Sahoo
{"title":"(咪唑-2-亚基)→S 配位相互作用及其在 S 氧化作用下的调制","authors":"Joy Mukhopadhyay, Prasad V. Bharatam, Subash Chandra Sahoo","doi":"10.1039/d4dt02286f","DOIUrl":null,"url":null,"abstract":"(NHC)→E coordination interactions are being explored in many chemical species, including carbones, and nitreones. (NHC)→S interactions are rare, but increasing attention is being paid to the compounds containing such interactions. The electron deficiency at the S centre is responsible for triggering electron donation from the NHC unit in (NHC)→SR(+) systems. It is well known that the positive charge at the sulfur centre increases upon single oxidation and further increases upon double oxidation. This implies that (NHC)→S interactions may get explicit after S-oxidation in (NHC)→SR(+) systems. To explore this hypothesis, we performed quantum chemical design and synthesis of (NHC)→SR(+), (NHC)→S(O)R(+), (NHC)→S(O)2R(+) complexes in which the ligands are imidazol-2-ylidene derivatives. Eight derivatives of (imidazol-2-ylidene)→SR(+) systems were generated, and their sulfoxide and sulfone derivatives were obtained by oxidising using (Urea-H2O2 and mCPBA, respectively). The crystal structures of three compounds belonging to a series were obtained. A comparison of the geometric, energetic and electronic characteristics confirmed the hypothesis that the (NHC)→S coordination interaction becomes comparatively stronger with an increase in oxygen atoms at the sulfur centre.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"(Imidazol-2-ylidene)→S Coordination Interaction and its Modulation Upon S-Oxidation\",\"authors\":\"Joy Mukhopadhyay, Prasad V. Bharatam, Subash Chandra Sahoo\",\"doi\":\"10.1039/d4dt02286f\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"(NHC)→E coordination interactions are being explored in many chemical species, including carbones, and nitreones. (NHC)→S interactions are rare, but increasing attention is being paid to the compounds containing such interactions. The electron deficiency at the S centre is responsible for triggering electron donation from the NHC unit in (NHC)→SR(+) systems. It is well known that the positive charge at the sulfur centre increases upon single oxidation and further increases upon double oxidation. This implies that (NHC)→S interactions may get explicit after S-oxidation in (NHC)→SR(+) systems. To explore this hypothesis, we performed quantum chemical design and synthesis of (NHC)→SR(+), (NHC)→S(O)R(+), (NHC)→S(O)2R(+) complexes in which the ligands are imidazol-2-ylidene derivatives. Eight derivatives of (imidazol-2-ylidene)→SR(+) systems were generated, and their sulfoxide and sulfone derivatives were obtained by oxidising using (Urea-H2O2 and mCPBA, respectively). The crystal structures of three compounds belonging to a series were obtained. A comparison of the geometric, energetic and electronic characteristics confirmed the hypothesis that the (NHC)→S coordination interaction becomes comparatively stronger with an increase in oxygen atoms at the sulfur centre.\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2024-09-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4dt02286f\",\"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":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4dt02286f","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
(Imidazol-2-ylidene)→S Coordination Interaction and its Modulation Upon S-Oxidation
(NHC)→E coordination interactions are being explored in many chemical species, including carbones, and nitreones. (NHC)→S interactions are rare, but increasing attention is being paid to the compounds containing such interactions. The electron deficiency at the S centre is responsible for triggering electron donation from the NHC unit in (NHC)→SR(+) systems. It is well known that the positive charge at the sulfur centre increases upon single oxidation and further increases upon double oxidation. This implies that (NHC)→S interactions may get explicit after S-oxidation in (NHC)→SR(+) systems. To explore this hypothesis, we performed quantum chemical design and synthesis of (NHC)→SR(+), (NHC)→S(O)R(+), (NHC)→S(O)2R(+) complexes in which the ligands are imidazol-2-ylidene derivatives. Eight derivatives of (imidazol-2-ylidene)→SR(+) systems were generated, and their sulfoxide and sulfone derivatives were obtained by oxidising using (Urea-H2O2 and mCPBA, respectively). The crystal structures of three compounds belonging to a series were obtained. A comparison of the geometric, energetic and electronic characteristics confirmed the hypothesis that the (NHC)→S coordination interaction becomes comparatively stronger with an increase in oxygen atoms at the sulfur centre.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.