DFT-studies of cis- and trans-[Rh(CO)2X2]+ (X = PH3, PF3, PC13, PBr3 PI3 or P(CH3)3) and oxidative addition of CH3I to them

Tapani Kinnunen, Kari Laasonen*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

13 Citations (Scopus)


We have performed B3LYB density functional calculations for oxidative addition of CH3I to [Rh(CO)2X2]+ (X = PH3, PF3, PCl3, PBr3, PI3 or P(CH3)3). This species is similar to the catalyst used in industrially important Monsanto process. Our goal is to see if the catalytic process could be enhanced by modifying the ligands. We have taken a set of phophine ligands and calculated the oxidative addition of methyl iodide to both the cis - and trans-forms of the modified catalysts. In our calculations, we found concerted mechanisms for the oxidative additions studied. Our results show that the activation parameters of the oxidative additions have a clear correlation to the ligand type and ligand size. With PCl3 and PBr3, our results show lower activation parameters than for the experimentally observed cis-[Rh(CO)2I2]-.

Original languageEnglish
Pages (from-to)150-155
Number of pages6
JournalJournal of Organometallic Chemistry
Issue number1-2
Publication statusPublished - 3 Jan 2003
MoE publication typeA1 Journal article-refereed


  • Carbonylation
  • Catalysis
  • Density funtional theory
  • Oxidative addition
  • Phosphine
  • Rhodium


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