THEORETICAL STUDY OF THE PH3-ASSISTED MIGRATION OF A COORDINATED ARYL GROUP TO A COORDINATED CO IN THE COMPLEXES RhCpI(CO)(p-XC6H4)
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 stud...
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| Autores principales: | , , |
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| Lenguaje: | English |
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Sociedad Chilena de Química
2017
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| Materias: | |
| Acceso en línea: | http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072017000200007 |
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| Sumario: | 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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