The air-stable complex Cp(PMe(3))IrCl(2) efficiently catalyzes the exchange of deuterium from D(2)O into both activated and unactivated C-H bonds of organic molecules without added acid or stabilizers. Selectivity is observed in many cases, with activation of primary C-H bonds occurring preferentially. A number of new stoichiometric transformations involving the iridiym catalyst precursor are also presented, including an oxidation-decarbonylation reaction with primary alcohols.