Theoretical study of the ph3-assisted migration of a coordinated aryl group to a coordinated co in the complexes rhcpi(co)(p-xc6h4)

• REZA GHIASI ^[1] ; NASRIN SADEGHI ^[1] ; SAEID JAMEHBOZORGI ^[1]
  1. [1] Islamic Azad University

     Islamic Azad University

     Irán

     
• Localización: Journal of the Chilean Chemical Society (Boletín de la Sociedad Chilena de Química), ISSN-e 0717-6309, ISSN 0366-1644, Vol. 62, Nº. 2, 2017, págs. 3454-3461
• Idioma: inglés
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• Resumen

  • We report the results of theoretical mechanistic studies on PH3-assisted migration of a coordinated aryl group to a coordinated CO in the complexes RhCpI(CO) (p-XC6H4). The X-substituent effect on thermodynamic and kinetic parameters was explored. The progress of the reaction was quantitatively studied using the bond orders of the Rh-CO bond, and the percentages of bond cleavage (BCij) of Rh-CO bond at the transition state were described. This theoretical study indicates good relationships between barrier energy (ΔE), bond distances variations (Rh-CO and Rh-Ph), activation energy (ΔH‡) , activation free energy (ΔG‡) values with Hammett constants of X-substituents. Linear relationship between ln(k) and the 103Rh magnetic shielding tensors of the product was explored.