University of Oulu

DOI:10.1039/d0cy01647k

Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes

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Author: Tolley, Lewis C.1; Fernández, Israel2; Bezuidenhout, Daniela I.1,3;
Organizations: 1Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, South Africa
2Departamento de Química Orgánica I and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Madrid, Spain
3Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O Box 3000, FI-90014 Oulu, Finland
4Institute of Advance Materials (INAM), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Jaume I, Avenida Vicente Sos Baynat s/n, 12071 Castellón, Spain
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 1.7 MB)
Persistent link: http://urn.fi/urn:nbn:fi-fe2020112592978
Language: English
Published: Royal Society of Chemistry, 2020
Publish Date: 2020-11-25
Description:

Abstract

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.

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Series: Catalysis science & technology
ISSN: 2044-4753
ISSN-E: 2044-4761
ISSN-L: 2044-4753
DOI: 10.1039/D0CY01647K
OADOI: https://oadoi.org/10.1039/D0CY01647K
Type of Publication: A1 Journal article – refereed
Field of Science: 116 Chemical sciences
Subjects:
Funding: 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.
Copyright information: © The Royal Society of Chemistry 2020. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
  https://creativecommons.org/licenses/by/3.0/