Chemistry of Metal Hydrides. XIV. Insertion Reactions of an Iridium(III) Hydride

Abstract

Del-'ot.t17zetrt of'Chet~~istq~, Ut~i~'rr.sity of' Wr.ste~.rr Ot~torio, Lot~dor~, 011to1,io Received November 27, 1972 The iridi~lm(II1) hydride, IrHCI2 {P(C2H5),},, gave 1 : I insertion products with perfl~~oropropene and 3,3,3-tdfluoropropynecontaining two and three phosphines per i r i d i~~m respectively. With tetrafluoroethylene, or 1,l-difluoroethylene a simple fluorine -hydridic hydrogen exchange reaction appears to occur. An unusual tricyanovinylic derivative is obtained as a major product of the reaction with tetracyanoethylene, while dimethylacetylene dicarboxylate gave an interesting p r o d~~c t containing two acetylene molecules per molecule of hydride. This is fornl~llated as the x-acetylenic complex of' the vinylic insertion product. The importance of ligand dissociation in these insertion processes is discussed. [Traduit par le journal]Can.

Experimental and Computational Investigation of the Aerobic Oxidation of a Late Transition Metal-Hydride

“…Furthermore, the solution IR spectrum of 3 (CH 2 Cl 2 ) features an Ir−H stretching frequency of 2161 cm −1 , slightly lower than the 2194 cm −1 observed for 1. 82,83 Remarkably, exposure of 3 to O 2 (1−5 atm) in C 6 D 6 between the temperature range 25−60 °C resulted in absolutely no reaction (up to 24 h).…”

Formate-driven catalysis and mechanism of an iridium–copper complex for selective aerobic oxidation of aromatic olefins in water

“…The UV-vis absorption spectral changes observed here are consistent with the catalytic results that the addition of an excess of 3 improves the yield of AcetophS due to preservation of the Ir(H)-Cu active structure.Based on the UV-vis spectral changes of 1 observed in formate buffer under Ar, the Ir(H)-Cu can be assumed to react with *)Ir(C 8 H 8 SO 3 )(bpp)Cu(dipic)] -(Ir(EtBnS)-Cu) (Scheme 1). Olefin insertion into the M-H bond of mononuclear metal complexes has been previously reported to form iridium-alkyl species [38][39][40][41]. The formation of Ir(EtBnS)-Cu was supported by our electron-spray ionization mass spectrometry (ESI-MS) measurements in which a peak cluster at m/z = 1006.96,assigned to be [[(Cp*)Ir(C 8 H 8 SO 3 )(bpp)Cu(dipic)] -+ HCOOH] -(calcd.…”