165271-75-0Relevant academic research and scientific papers
Novel synthetic route to vinylidenerhodium(I) and -iridium(I) complexes using vinyl chlorides as substrates
Wolf, Justin,Lass, Raimund W.,Manger, Matthias,Werner, Helmut
, p. 2649 - 2651 (2008/10/09)
The bis(triisopropylphosphine)rhodium(I) and -iridium(I) compounds [RhCl(PiPr3)2]n (1) and [IrCl(C8H14)(PiPr3)2] (2) react with 2 equiv of RR′C=CHCl and 2 equiv of Na in benzene at room temperature to give the vinylidene complexes trans-[MCl(=C=CRR′)(PiPr3)2] (3-7) in moderate to good yields. From 2, Ph2C=CHCl, and Na, the alkyne derivative trans-[IrCl(PhC≡CPh)(PiPr3)2] (8) is obtained as the main product. Preliminary studies aimed to elucidate the mechanism of the reaction indicate that from RR′C=CHCl and Na a vinyl radical RR′C=CH? is possibly formed which, depending on the substituents R and R′, either reacts to give the alkyne RC≡CR′, initiates polymerization, or attacks the metal center of the starting material, to give the metal vinylidenes.
