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

The iridium(III) hydride, IrHCl2 {P(C2H5)3}3, gave 1:1 insertion products with perfluoropropene and 3,3,3-trifluoropropyne containing two and three phosphines per iridium respectively. With tetrafluoroethylene, or 1,1-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 product containing two acetylene molecules per molecule of hydride. This is formulated as the π-acetylenic complex of the vinylic insertion product. The importance of ligand dissociation in these insertion processes is discussed.