Kinetic study of the oxidative addition reaction between methyl iodide and [Rh(imino-β-diketonato)(CO)(PPh)3] complexes, utilizing UV–vis, IR spectrophotometry, NMR spectroscopy and DFT calculations

dc.contributor.authorFerreira, Hendrik
dc.contributor.authorConradie, Marrigje Marianne
dc.contributor.authorConradie, Jeanet
dc.date.accessioned2022-03-17T06:08:27Z
dc.date.available2022-03-17T06:08:27Z
dc.date.issued2022
dc.description.abstractThe oxidative addition of methyl iodide to [Rh(β-diketonato)(CO)(PPh)3] complexes, as modal catalysts of the first step during the Monsanto process, are well-studied. The β-diketonato ligand is a bidentate (BID) ligand that bonds, through two O donor atoms (O,O-BID ligand), to rhodium. Imino-β-diketones are similar to β-diketones, though the donor atoms are N and O, referred to as an N,O-BID ligand. In this study, the oxidative addition of methyl iodide to [Rh(imino-β-diketonato)(CO)(PPh)3] complexes, as observed on UV–Vis spectrophotometry, IR spectrophotometry and NMR spectrometry, are presented. Experimentally, one isomer of [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] and two isomers of [Rh(CH3COCHCNHCH3)(CO)(PPh3)] are observed—in agreement with density functional theory (DFT) calculations. Experimentally the [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] + CH3I reaction proceeds through one reaction step, with a rhodium(III)-alkyl as the final reaction product. However, the [Rh(CH3COCHCNHCH3)(CO)(PPh3)] + CH3I reaction proceeds through two reaction steps, with a rhodium(III)-acyl as the final reaction product. DFT calculations of all the possible reaction products and transition states agree with experimental findings. Due to the smaller electronegativity of N, compared to O, the oxidative addition reaction rate of CH3I to the two [Rh(imino-β-diketonato)(CO)(PPh)3] complexes of this study was 7–11 times faster than the oxidative addition reaction rate of CH3I to [Rh(CH3COCHCOCH3)(CO)(PPh3)].en_ZA
dc.description.versionPublisher's versionen_ZA
dc.identifierhttps://doi.org/10.3390/molecules27061931
dc.identifier.citationFerreira, H., Conradie, M.M., & Conradie, J. (2022). Kinetic study of the oxidative addition reaction between methyl iodide and [Rh(imino-β-diketonato)(CO)(PPh)3] complexes, utilizing UV–vis, IR spectrophotometry, NMR spectroscopy and DFT calculations. Molecules, 27, 1931. https://doi.org/10.3390/molecules27061931en_ZA
dc.identifier.issn1420-3049
dc.identifier.urihttp://hdl.handle.net/11660/11543
dc.language.isoenen_ZA
dc.publisherMDPIen_ZA
dc.rights.holderAuthor(s)en_ZA
dc.rights.licensehttps://creativecommons.org/licenses/by/4.0/
dc.subjectRhodiumen_ZA
dc.subjectImino-β-diketonatoen_ZA
dc.subjectOxidative additionen_ZA
dc.subjectDFTen_ZA
dc.titleKinetic study of the oxidative addition reaction between methyl iodide and [Rh(imino-β-diketonato)(CO)(PPh)3] complexes, utilizing UV–vis, IR spectrophotometry, NMR spectroscopy and DFT calculationsen_ZA
dc.typeArticleen_ZA
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