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• W2141624178 abstract "Sequential addition of CO molecules to cationic aryl–hydrido RhIII complexes of phosphine-based (PCP) pincer ligands was found to lead first to CH reductive elimination and then to CH oxidative addition, thereby demonstrating a dual role of CO. DFT calculations indicate that the oxidative addition reaction is directly promoted by CO, in contrast to the commonly accepted view that CO hinders such reactions. This intriguing effect was traced to repulsive π interactions along the aryl-Rh-CO axis, which are augmented by the initially added CO ligand (due to antibonding interactions between occupied Rh dπ orbitals and occupied π orbitals of both CO and the arene moiety), but counteracted by the second CO ligand (due to significant π back-donation). These repulsive interactions were themselves linked to significant weakening of the π-acceptor character of CO in the positively charged rhodium complexes, which is concurrent with an enhanced σ-donating capability. Replacement of the phosphine ligands by an analogous phosphinite-based (POCOP) pincer ligand led to significant changes in reactivity, whereby addition of CO did not result in CH reductive elimination, but yielded relatively stable mono- and dicarbonyl aryl–hydrido POCOP–RhIII complexes. DFT calculations showed that the stability of these complexes arises from the higher electrophilicity of the POCOP ligand, relative to PCP, which leads to partial reduction of the excessive π-electron density along the aryl-Rh-CO axis. Finally, comparison between the effects of CO and acetonitrile on CH oxidative addition revealed that they exhibit similar reactivity, despite their markedly different electronic properties. However, DFT calculations indicate that the two ligands operate by different mechanisms." @default.
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• W2141624178 date "2010-01-04" @default.
• W2141624178 modified "2023-09-25" @default.
• W2141624178 title "Effect of CO on the Oxidative Addition of Arene CH Bonds by Cationic Rhodium Complexes" @default.
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• W2141624178 cites W1966235871 @default.
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• W2141624178 cites W1978008449 @default.
• W2141624178 cites W1980617928 @default.
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• W2141624178 doi "https://doi.org/10.1002/chem.200901526" @default.
• W2141624178 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19918810" @default.
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