Substitution and Isomerization of Asymmetric β-Diketonato Rhodium(I) Complexes: A Crystallographic and Computational Study

Ligand substitution of PPh3 for CO in the asymmetric square-planar β-diketonato complex [Rh(PhCOCHCOCH2CH3)(CO)2] leads to formation of the monosubstituted [Rh(PhCOCHCOCH2CH3)(CO)(PPh3)] product. Two geometrical product isomers are possible, which unexpectedly crystallize in the same crystal lattice...

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Bibliographic Details
Published inOrganometallics Vol. 29; no. 11; pp. 2446 - 2458
Main Authors Hopmann, Kathrin H, Stuurman, Nomampondomise F, Muller, Alfred, Conradie, Jeanet
Format Journal Article
LanguageEnglish
Published American Chemical Society 14.06.2010
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Summary:Ligand substitution of PPh3 for CO in the asymmetric square-planar β-diketonato complex [Rh(PhCOCHCOCH2CH3)(CO)2] leads to formation of the monosubstituted [Rh(PhCOCHCOCH2CH3)(CO)(PPh3)] product. Two geometrical product isomers are possible, which unexpectedly crystallize in the same crystal lattice. DFT calculations of the substitution reaction support a two-step mechanism, involving temporary dissociation of a β-diketonato ligand and formation of a square-planar intermediate. Analysis of the mechanisms involved in product isomerization suggests several noncatalyzed and solvent-assisted interconversion pathways.
ISSN:0276-7333
1520-6041
DOI:10.1021/om1000138