<div>The synthesis and characterization of an iridium polyhydride complex (Ir-H4)</div><div>supported by an electron-rich PCP framework is described. This complex readily loses molecular</div><div>hydrogen allowing for rapid room temperature hydrogen isotope exchange (HIE) at the hydridic</div><div>positions and the α-C-H site of the ligand with deuterated solvents such as benzene-d6, toluene-d8</div><div>and THF-d8. The removal of 1-2 equivalents of molecular H2 forms unsaturated iridium carbene</div><div>trihydride (Ir-H3) or monohydride (Ir-H) compounds that are able to create further unsaturation</div><div>by reversibly transferring a hydride to the ligand carbene carbon. These species are highly active</div><div>hydrogen isotope exchange (HIE) catalysts using C6D6 or D2O as deuterium sources for the</div><div>deuteration of a variety of substrates. By modifying conditions to influence the Ir-Hn speciation,</div><div>deuteration levels can range from near exhaustive to selective only for sterically accessible sites.</div><div>Preparative level deuterations of select substrates were performed allowing for procurement of</div><div>>95% deuterated compounds in excellent isolated yields; the catalyst can be regenerated by</div><div>treatment of residues with H2 and is still active for further reactions.</div>