title: Thione complexes of Rh(I): a first comparison with the bonding and catalytic activity of related carbene and imine compounds.
abstract: Heterocyclic 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(eta(4)-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 degrees C, 8 MPa CO-H2(1:1), 16 h, 1:1000 catalyst to 1-hexene ratio.
authors.affiliation: Department of Chemistry, University of Stellenbosch, Private Bag X1, Matieland, 7602, Stellenbosch, South Africa.
authors.forename: Arno
authors.initials: A
authors.lastname: Neveling
authors.forename: Gerrit R
authors.initials: GR
authors.lastname: Julius
authors.forename: Stephanie
authors.initials: S
authors.lastname: Cronje
authors.forename: Catharine
authors.initials: C
authors.lastname: Esterhuysen
authors.forename: Helgard G
authors.initials: HG
authors.lastname: Raubenheimer