A synthetic route to a new iridium(III) complex containing a novel proton hydride bonding interaction has been established. fac-IrH3(PPh(3))(3) reacts with 2-mercaptopyridine HSpy (Spy = 2-SC5H4N) to give the known dihydride Ir(H)(2)(eta(2)-Spy)(PPh(3))(2) 8. Ir(H)(2)(eta(2)-Spy)(PPh(3))(2) reacts with HSpy . HBF4 to give [IrH(eta(1)-SC5H4NH)(eta(2)-SC5H4N)(PPh(3))(2)](BF4) 9 which possesses a unique bifurcated hydrogen bonding interaction involving Ir-H ... H(N)... F-B atoms with the distances of 2.0(1) Angstrom for the H ... H unit and of 2.0(1) Angstrom for the F ... H unit in the crystalline state, In solution the N-H ... H-Ir interaction is maintained according to H-1 T-1(min) and nOe measurements. Isotope shifts in the chemical shifts of the hydride and one phosphorus of 9 have been observed in H-1 and P-31{H-1} NMR spectra of [IrH(eta(1)-SC5H4ND)(eta(2)-SC5H4N)(PPh(3))(2)](BF4), 9-d(1), prepared by the reaction of 9 with MeOD or CF3CO2D. The crystal and molecular structure of [IrH(eta(1)-SC5H4NH)(eta(2)-SC5H4N)(PPh(3))(2)](BF4). 0.5C(6)H(6) 9 has been solved by X-ray analysis : monoclinic space group P2(1)/c with a = 17.723(3) Angstrom, b = 10.408(1) Angstrom, c = 26.073(4) Angstrom beta = 108.08(1)degrees, V = 4572.0(11) Angstrom(3), and Z = 4, The known complex fac-IrH3(PPh(3))(3), 7, is made by a new and improved method by reacting mer-IrHCl2(PPh(3))(3) with NaOEt and H-2(g), VT-H-1 NMR spectra (+90 to -80 degrees C) of the hydrides of 7 reveal that the J(AA) and J(AX) couplings change in the AA’A " XX’X " pattern (A = H-1, X = P-31) but that the complex is not fluxional. The T-1(min) value of 0.144 s for the hydrides of 7 at -60 degrees C (300 MHz) indicates that the shortest H-H distances are about 1.8 Angstrom.