42482-33-7Relevant academic research and scientific papers
Formation of carbon-carbon bonds by oxidative-addition reactions to trans-MeIr(CO)(P(p-tolyl)3)2
Thompson, Jeffrey S.,Atwood, Jim D.
, p. 3525 - 3529 (2008/10/08)
Oxidative addition of various organic halides to trans-Ir(CO)(Me)(P(p-tolyl)3)2 has been examined by variable-temperature NMR spectroscopy. For PhCH2Cl, CH3C(O)Cl, Ph2CHC(O)Cl, PhC(O)Cl, and PhCH2C(O)Cl oxidative addition is followed by reductive elimination to form carbon-carbon bonds. For reaction of trans-Ir(CO)(Me)(P(p-tolyl)3)2 with CH3C(O)Cl the intermediate is characterized by 1H and 31P NMR spectroscopy at -5°; acetone elimination is significant at 10°C. For the other complexes the oxidative addition is sufficiently slow that an intermediate cannot be identified. Oxidative addition of MeI and EtI to trans-MeIr(CO)(P(p-tolyl)3)2 leads to complexes Ir(CO)(I)(R)(Me)(P(p-tolyl)3)2 that are characterized by 1H and 31P NMR spectroscopy. For R = Me this complex is stable; for R = Et the complex slowly undergoes β-elimination leading to C2H4 and CH4. These results provide strong support for a mechanism involving halide dissociation from the iridium(III) complexes.
Bond-forming reactions to a coordinated hydroxo group: Reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with MeI, EtI, HCl, CH3C(O)Cl, and H2
Thompson, Jeffrey S.,Randall, Sherri L.,Atwood, Jim D.
, p. 3906 - 3910 (2008/10/08)
Reactions of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with MeI, EtI, HCl, and CH3C(O)Cl lead to the formation of bonds between the hydroxide and the adding group. For MeI and EtI addition, where the alcohols are formed, the reactions occur by oxidative addition followed by reductive elimination to form the carbon-oxygen bond. Reaction with HCl proceeds very rapidly by protonation of the hydroxide to eliminate H2O. The reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with acetyl chloride gives a mixture of products from initial attack of acetyl chloride on the hydroxide to produce acetic acid. Subsequent oxidative addition of the acid produces an acetate complex. Reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with H2 produces the trihydride H3Ir(CO)(P(p-tolyl)3)2 and H2O. This reaction is partially reversible; treatment of the trihydride with H2O produces the hydroxy complex. The reactions reported here are among the first that exhibit bond formation to a metal-bound hydroxo group.
