A hemilabile and cooperative N-donor functionalized 1,2,3-triazol- 5-ylidene ligand for selective and base-free rhodium(I) catalyzed alkyne hydrothiolation reactions

dc.contributor.authorStrydom, Ian
dc.contributor.authorGuisado-Barrios, Gregorio
dc.contributor.authorFernandez, Israel
dc.contributor.authorLiles, David C.
dc.contributor.authorPeris, Eduardo
dc.contributor.authorBezuidenhout, Daniela Ina
dc.date.accessioned2017-04-20T16:43:02Z
dc.date.issued2017-01
dc.description.abstractA series of novel cationic and neutral Rh-complexes with an N-donor functionalized 1,2,3-triazol-5-ylidene (TRZ) ligand (where pendant N-donor is NHBoc, NH2 or NMe2 respectively) is described. Their catalytic activity was evaluated towards the hydrothiolation of alkynes. Among the catalysts, a neutral dicarbonyl complex featuring the tethered-NBoc amido-TRZ ligand proved very selective for alkyne hydrothiolation with an aryl thiol. Remarkably, the reaction could be carried out in the absence of pyridine or base additive. In addition, during the reaction course, no evidence for oxidative addition of the thiol S-H was observed, strongly suggesting a reaction pathway whereby a bifunctional ligand is involved. Experimental and theoretical mechanistic investigations suggest a ligand-assisted deprotonation of substrate thiol, hemilabile dissociation of amine from metal and thiolate coordination, which is indicative of a different reaction mechanism to those previously reported for related alkyne hydrothiolation reaction.en_ZA
dc.description.departmentChemistryen_ZA
dc.description.embargo2018-01-31
dc.description.librarianhb2017en_ZA
dc.description.sponsorshipG. G.-B. thanks the MINECO for a postdoctoral grant (FPDI- 2013-16525) and Generalitat Valenciana (GV/2015/097) for financial support. E.P and I.F. gratefully acknowledge financial support from the Spanish MINECO-FEDER (CTQ2014-51999-P to E.P. and CTQ2013-44303-P and CTQ2014-51912-REDC to I.F.), UJI (P11B2014-02 to E.P.). D.I.B and I.S. gratefully acknowledge the National Research Foundation, South Africa (NRF 87890, 103698 and 92521), and Sasol Technology R&D Pty. Ltd., South Africa for financial support.en_ZA
dc.description.urihttp://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3765en_ZA
dc.identifier.citationStrydom, I, Guisado-Barrios, G, Fernandez, I, Liles, DC, Peris, E & Bezuidenhout, DI 2017, 'A hemilabile and cooperative N-donor functionalized 1,2,3-triazol- 5-ylidene ligand for selective and base-free rhodium(I) catalyzed alkyne hydrothiolation reactions', Chemistry - A European Journal, vol. 23, no. 6, pp. 1393-1401.en_ZA
dc.identifier.issn0947-6539 (print)
dc.identifier.issn1521-3765 (online)
dc.identifier.other10.1002/chem.201604567
dc.identifier.urihttp://hdl.handle.net/2263/60004
dc.language.isoenen_ZA
dc.publisherWileyen_ZA
dc.rights© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the pre-peer reviewed version of the following article : A hemilabile and cooperative N-donor functionalized 1,2,3-triazol-5-ylidene ligand for selective and base-free rhodium(I) catalyzed alkyne hydrothiolation reactions, Chemistry - A European Journal, vol. 23, no. 6, pp. 1393-1401, 2017. doi : 10.1002/chem.201604567. The definite version is available at : http://onlinelibrary.wiley.comjournal/10.1002/(ISSN)1521-3765.en_ZA
dc.subjectN-donor functionalizeden_ZA
dc.subjectBase-free rhodium(I)en_ZA
dc.subjectAlkyne hydrothiolation reactionsen_ZA
dc.titleA hemilabile and cooperative N-donor functionalized 1,2,3-triazol- 5-ylidene ligand for selective and base-free rhodium(I) catalyzed alkyne hydrothiolation reactionsen_ZA
dc.typePostprint Articleen_ZA

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