Thione complexes of Rh(I): A first comparison with the bonding and catalytic activity of related carbene and imine compounds

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dc.contributor.authorNeveling A.
dc.contributor.authorJulius G.R.
dc.contributor.authorCronje S.
dc.contributor.authorEsterhuysen C.
dc.contributor.authorRaubenheimer H.G.
dc.date.accessioned2011-05-15T15:59:07Z
dc.date.available2011-05-15T15:59:07Z
dc.date.issued2005
dc.description.abstractHeterocyclic mono(thione), trans-bis(thione), cis-bis(thione), trans-(carbene-thione), cis-(carbene-thione), trans-(phosphine-thione) and mono(imine) complexes of rhodium(I) have been prepared and fully characterised. Chloro(η4-1,5-cyclooctadiene)(L)rhodium(I) (1a, L = 1,3-diisopropyl-4,5-dimethyl-2,3-dihydro-1H-imidazol-2-thione; 1b, L = 1,3,4,5-tetramethyl-2,3-dihydro-1H-imidazol-2-thione) appear as isomers at room temperature due to slow coordination exchange on the S-donor atom. In the three structures determined, the substituent on the sulfur appears syn to Cl. Hindered rotation about the Rh-carbene bond is revealed in the NMR spectra of seven new complexes with isopropyl substituents on the heterocyclic carbene ligands. The trans influence of the thione ligands is smaller than that of carbenes but larger than that shown by imines and chloride. Thione complexes are better catalyst precursors than the carbene complexes for the hydroformylation of 1-hexene under the chosen reaction conditions: 80°C, 8 MPa CO-H2 (1 : 1), 16 h, 1 : 1000 catalyst to 1-hexene ratio.
dc.description.versionArticle
dc.identifier.citationDalton Transactions
dc.identifier.citation1
dc.identifier.issn14779226
dc.identifier.other10.1039/b414040k
dc.identifier.urihttp://hdl.handle.net/10019.1/11010
dc.subjectCatalysis
dc.subjectCatalyst activity
dc.subjectChemical bonds
dc.subjectComplexation
dc.subjectCrystal structure
dc.subjectNuclear magnetic resonance spectroscopy
dc.subjectCarbene
dc.subjectImine compounds
dc.subjectThione complexes
dc.subjectRhodium
dc.titleThione complexes of Rh(I): A first comparison with the bonding and catalytic activity of related carbene and imine compounds
dc.typeArticle
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