RESEARCH ARTICLE

 

Methyl iodide oxidative addition to rhodium(I) complexes: A DFT and NMR study of [Rh(FcCOCHCOCf₃)(CO)(pph₃)] and the rhodium(III) reaction products

 

 

Marrigje M. Conradie; Jeanet Conradie^*

Department of Chemistry, University of the Free State, Bloemfontein, 9301 South Africa

 

 

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ABSTRACT

A theoretical (DFT) study of the equilibrium geometry of the possible reaction products of the oxidative addition reaction [Rh(FcCOCHCOCF₃)(CO)(PPh₃)] + CH₃I (Fc = ferrocenyl), consistent with experimental observations, revealed that the first alkyl product results from trans addition to Rh^I. Isomerization via an acyl intermediate leads to a second octahedral alkyl product with the PPh₃ group and the iodide above and below the square plane. Theoretical computations also revealed that the thermodynamic acyl product adopts a square-pyramidal geometry with the COCH₃ group in the apical position.

Keywords: DFT, computational, rhodium, β-diketone, NMR

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Full text available only in pdf format.

 

Acknowledgements

Financial assistance by the South African National Research Foundation, under grant number 2067416, and the Central Research Fund of the University of the Free State is gratefully acknowledged.

 

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Received 8 February 2008
Revised 18 June 2008
Accepted 12 September 2008

 

 

* To whom correspondence should be addressed. E-mail: conradj.sci@ufs.ac.za