Iridium complexes containing the large bite angle bisphosphine ligand xantphos have been synthesized and their reactivity studied. Several of these complexes are the first reported Ir(xantphos) systems to be characterized by X-ray diffraction. Variable-temperature NMR spectroscopic studies of IrI(CO)(2)(xantphos) (1-I) and Ir(COEt)(CO)(2)(xantphos) (8) show two separate dynamic processes in which the phosphorus donors and the backbone methyl groups of the xantphos ligand are exchanged. The addition of parahydrogen (p-H-2) to 1-I leads to the formation of two dihydride isomers including one in which both hydride ligands are trans to the phosphorus donors, suggestive of an Ir(I) xantphos intermediate with the ligand chelated in a trans-spanning fashion (2b). The bromide and chloride Ir(I) analogues (1-Br and 1-Cl) also form this isomer upon reaction with parahydrogen, with 1-Cl yielding only this dihydride species. The trihydride complex IrH3(CO)(xantphos) (7) has been prepared, and its exchange with free hydrogen at elevated temperature is confirmed by reaction with p-H2. The hydride complexes IrH(CO)(2)(xantphos) (6) and IrH3(CO)( xantphos) (7), as well as the propionyl complex 8, are modest catalysts for the hydroformylation of 1-hexene and styrene under mild conditions. The addition of p-H2 to 8 permits direct observation of the propionyl dihydride species IrH2(COEt)(CO)(xantphos) (9) under both thermal and photolytic conditions, as well as unusual but weak polarization of the aldehydic proton of the propanal product that forms upon reductive elimination from 9.