Tetrafluoroethyl complexes derived from insertion of the tetrafluoroethylene ligand into an iridium-hydride bond

Article abstract of DOI:10.1021/om00156a034

The reaction of IrH(CO)(PPh₃)₃ with tetrafluoroethylene gives the hydride olefin complex IrH-(C₂F₄)(CO)(PPh₃)₂. Further reactions of IrH(C₂F₄)(CO)(PPh₃)₂ with a coordinating ligand L (L = C₂F₄, CO, C₂H₄) result in the insertion of the coordinated olefin into the iridium-hydrogen bond and formation of tetrafluoroethyl complexes, Ir(CF₂CF₂H)(L)(CO)(PPh₃)₂. Thermal displacement of the ethylene ligand in Ir(CF₂CF₂H)(C₂H₄)(CO)(PPh ₃)₂ gives the four-coordinate complex Ir(CF₂CF₂H)(CO)(PPh₃)₂. The X-ray crystal structure of the dicarbonyl complex Ir(CF₂CF₂H)(CO)₂(PPh₃)₂ is described. Ir(CF₂CF₂H)(CO)₂(PPh₃)₂ crystallizes in the triclinic space group P1 with a = 9.868 (5) ?, b = 11.5727 (5) ?, c = 17 083 (9) ? α = 103.9 (4)°, β = 94.14 (4)°, γ = 113.09 (3)°, and Z = 2 with d(calcd) = 1.699 g cm^-3 for a molecular weight of 873.83. The structure was refined to give R = 0.0400 and R_w = 0.0407, and in contrast to the geometry displayed in solution, which has trans triphenylphosphines, has a cis arrangement of triphenylphosphine ligands. The Ir-CF₂CF₂H bond distance is 2.145 (8) ?.