NDLI: Effect of CO on the Oxidative Addition of Arene CH Bonds by Cationic Rhodium Complexes

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Effect of CO on the Oxidative Addition of Arene CH Bonds by Cationic Rhodium Complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Cohen, Revital Shimon, Linda J. W. Efremenko, Irena Milstein, David Montag, Michael Ben-david, Yehoshoa Salem, Hiyam Leitus, Gregory Diskin-posner, Yael Martin, Jan M. L.
Description	Author Affiliation: Montag M ( Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76000, Israel.)
Abstract	Sequential addition of CO molecules to cationic aryl–hydrido $Rh^{III}$ complexes of phosphine-based (PCP) pincer ligands was found to lead first to CH reductive elimination and then to CH 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 $d_{π}$ 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 CH reductive elimination, but yielded relatively stable mono- and dicarbonyl aryl–hydrido $POCOP–Rh^{III}$ 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 CH 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.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	1
Volume Number	16
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2010-01-04
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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