Substitution and isomerization of asymmetric β-diketonato rhodium(I) complexes: A crystallographic and computational study

Kathrin H. Hopmann; Nomampondomise F. Stuurman; Alfred Muller; Jeanet Conradie

doi:10.1021/om1000138

Substitution and isomerization of asymmetric β-diketonato rhodium(I) complexes: A crystallographic and computational study

Kathrin H. Hopmann, Nomampondomise F. Stuurman, Alfred Muller, Jeanet Conradie

Chemical Sciences

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28 Citations (Scopus)

Abstract

Ligand substitution of PPh₃ for CO in the asymmetric square-planar β-diketonato complex [Rh(PhCOCHCOCH₂CH ₃)(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.

Original language	English
Pages (from-to)	2446-2458
Number of pages	13
Journal	Organometallics
Volume	29
Issue number	11
DOIs	https://doi.org/10.1021/om1000138
Publication status	Published - 14 Jun 2010

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Substitution and isomerization of asymmetric β-diketonato rhodium(I) complexes: A crystallographic and computational study",

abstract = "Ligand substitution of PPh3 for CO in the asymmetric square-planar β-diketonato complex [Rh(PhCOCHCOCH2CH 3)(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.",

author = "Hopmann, \{Kathrin H.\} and Stuurman, \{Nomampondomise F.\} and Alfred Muller and Jeanet Conradie",

year = "2010",

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doi = "10.1021/om1000138",

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journal = "Organometallics",

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TY - JOUR

T1 - Substitution and isomerization of asymmetric β-diketonato rhodium(I) complexes

T2 - A crystallographic and computational study

AU - Hopmann, Kathrin H.

AU - Stuurman, Nomampondomise F.

AU - Muller, Alfred

AU - Conradie, Jeanet

PY - 2010/6/14

Y1 - 2010/6/14

N2 - Ligand substitution of PPh3 for CO in the asymmetric square-planar β-diketonato complex [Rh(PhCOCHCOCH2CH 3)(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.

AB - Ligand substitution of PPh3 for CO in the asymmetric square-planar β-diketonato complex [Rh(PhCOCHCOCH2CH 3)(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.

UR - https://www.scopus.com/pages/publications/77953202483

U2 - 10.1021/om1000138

DO - 10.1021/om1000138

M3 - Article

AN - SCOPUS:77953202483

SN - 0276-7333

VL - 29

SP - 2446

EP - 2458

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Substitution and isomerization of asymmetric β-diketonato rhodium(I) complexes: A crystallographic and computational study

Abstract

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