Methyl iodide oxidative addition to rhodium(I) complexes: A DFT and NMR study of [Rh(FcCOCHCOCf3)(CO)(pph3)] and the rhodium(III) reaction products
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 RhI. 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.
Main Authors: | , |
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Format: | Digital revista |
Language: | English |
Published: |
The South African Chemical Institute
2008
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Online Access: | http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502008000100019 |
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Summary: | 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 RhI. 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. |
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