| Abstract
| - Oxidative addition of methyl iodide to rhodium complexes, the first and rate-determiningstep in the rhodium-catalyzed methanol carbonylation process, has been studied computationally by means of DFT calculations including solvent effects. Monsanto's catalyst cis-[Rh(CO)2I2]-, Cole−Hamilton's trans-[Rh(PEt3)2(CO)I], and Freixa's new dirhodium [Rh2(μ-Cl)2(SPAN-PPh2)(CO)2] complexes were considered. Transition state structures determined in this study confirm the SN2 character of the reaction, i.e., the nucleophilic attackby the rhodium complex on MeI. The transition states show a linear arrangement of theI−CH3−Rh moiety. The DFT level of calculation and solvent effects were shown to be crucialin the determination of TS structures. Thermochemical parameters computed in this studywere in excellent agreement with experimental kinetic data.
- Oxidative addition of methyl iodide to mono- and dirhodium complexes was studied by means of DFT calculations including solvent effects. Optimized transition state structures confirm the SN2 character of the reaction and the linear arrangement of the I−CH3−Rh moiety. Activation parameters were in excellent agreement with experimental kinetic data.
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