JOURNAL OF CHILEAN CHEMICAL SOCIETY

Vol 62 No 2 (2017): Journal of the Chilean Chemical Society
Original Research Papers

THEORETICAL STUDY OF THE PH3-ASSISTED MIGRATION OF A COORDINATED ARYL GROUP TO A COORDINATED CO IN THE COMPLEXES RHCPI(CO)(P-XC6H4)

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  • Reza Ghiasi,
  • Nasrin Sadeghi,
  • Saeid Jamehbozorgi
Reza Ghiasi
Department of Chemistry, Faculty of science, Arak Branch, Islamic Azad University
Nasrin Sadeghi
Department of Chemistry, East Tehran Branch, Islamic Azad University
Saeid Jamehbozorgi
Department of chemistry, faculty of science, Hamedan Branch, Islamic Azad University
Published June 16, 2017
Keywords
  • Insertion reaction,
  • Substituent effect,
  • Thermodynamic parameters,
  • Kinetic parameters
How to Cite
Ghiasi, R., Sadeghi, N., & Jamehbozorgi, S. (2017). THEORETICAL STUDY OF THE PH3-ASSISTED MIGRATION OF A COORDINATED ARYL GROUP TO A COORDINATED CO IN THE COMPLEXES RHCPI(CO)(P-XC6H4). Journal of the Chilean Chemical Society, 62(2). Retrieved from https://jcchems.com/index.php/JCCHEMS/article/view/185

Copyright (c) 2017 Reza Ghiasi, Nasrin Sadeghi, Saeid Jamehbozorgi

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Abstract

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.

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