Kinetic Study of the Oxidative Addition Reaction between Methyl Iodide and [Rh(imino-β-diketonato)(CO)(PPh)3] Complexes, Utilizing UV-Vis, IR Spectrophotometry, NMR Spectroscopy and DFT Calculations

The oxidative addition of methyl iodide to [Rh(beta-diketonato)(CO)(PPh)(3)] complexes, as modal catalysts of the first step during the Monsanto process, are well-studied. The beta-diketonato ligand is a bidentate (BID) ligand that bonds, through two O donor atoms (O,O-BID ligand), to rhodium. Imino-beta-diketones are similar to beta-diketones, though the donor atoms are N and O, referred to as an N,O-BID ligand. In this study, the oxidative addition of methyl iodide to [Rh(imino-beta-diketonato)(CO)(PPh)(3)] complexes, as observed on UV-Vis spectrophotometry, IR spectrophotometry and NMR spectrometry, are presented. Experimentally, one isomer of [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] and two isomers of [Rh(CH3COCHCNHCH3)(CO)(PPh3)] are observed-in agreement with density functional theory (DFT) calculations. Experimentally the [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] + CH3I reaction proceeds through one reaction step, with a rhodium(III)-alkyl as the final reaction product. However, the [Rh(CH3COCHCNHCH3)(CO)(PPh3)] + CH3I reaction proceeds through two reaction steps, with a rhodium(III)-acyl as the final reaction product. DFT calculations of all the possible reaction products and transition states agree with experimental findings. Due to the smaller electronegativity of N, compared to O, the oxidative addition reaction rate of CH3I to the two [Rh(imino-beta-diketonato)(CO)(PPh)(3)] complexes of this study was 7-11 times faster than the oxidative addition reaction rate of CH3I to [Rh(CH3COCHCOCH3)(CO)(PPh3)].

Automated summary

This study investigates the oxidative addition of methyl iodide to [Rh(imino-beta-diketonato)(CO)(PPh)(3)] complexes through experimental and computational methods. The results demonstrate that the presence of nitrogen and oxygen donor atoms enhances the reaction rate. The experimental findings are in agreement with the computational results.