Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes
| العنوان: | Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes |
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| المؤلفون: | Israel Fernández, Lewis C. Tolley, Daniela Ina Bezuidenhout, Gregorio Guisado-Barrios |
| المساهمون: | National Research Foundation (South Africa), Sasol, Ministerio de Economía y Competitividad (España), Agencia Estatal de Investigación (España), Ministerio de Ciencia, Innovación y Universidades (España), European Commission |
| المصدر: | Repositori Universitat Jaume I Universitat Jaume I Digital.CSIC. Repositorio Institucional del CSIC instname |
| بيانات النشر: | The Royal Society of Chemistry, 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | Chemistry, Aryl, Thiophenol, Markovnikov's rule, chemistry.chemical_element, Medicinal chemistry, Catalysis, Rhodium, Catalytic activity, chemistry.chemical_compound, Iridium, Selectivity, Carbene |
| الوصف: | The catalytic activity of a set of mono- and bimetallic Rh(I) and Ir(I) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkynes. The hydrothiolation of 1-hexyne with thiophenol in the absence of an external base or other additives was selected as a model reaction. All rhodium complexes are highly selective catalysts towards Markovnikov product formation and display superior activity compared to the related iridium derivatives. DFT calculations were carried out to rationalize the reaction mechanism and selectivity of this process. Neutral dinuclear [Rh2Cl2(cod)2(μ-COC)] was found to be the most effective catalyst for this transformation. Its applicability was further studied towards the hydrothiolation of different alkyl and aryl alkynes using predominantly aryl thiols and proved to be one of the most active and selective catalysts towards the α-vinyl sulfide product to date. L. C. T. and D. I. B. acknowledge the National Research Foundation, South Africa (NRF 115642; NRF 94784; NRF 100119; NRF 111705), and Sasol Technology R&D Pty. Ltd. (South Africa) for financial support (D. I. B.). I. F. is grateful to the Spanish Ministerio de Economía y Competitividad and FEDER (Grants CTQ2016-78205-P, PID2019-106184GB-I00 and CTQ2016-81797-REDC). G. G.-B gratefully acknowledges MICIU/AEI/FEDER “Una manera de hacer Europa” (PGC2018-093382-B-I00 and RTI2018-098903-J-I00) for financial support. |
| وصف الملف: | application/pdf |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::88a060e5bb4a3713c764582fa7eec993 http://hdl.handle.net/10234/192842 |
| Rights: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....88a060e5bb4a3713c764582fa7eec993 |
| قاعدة البيانات: | OpenAIRE |
| الوصف غير متاح. |