SYNTHESIS, PROPERTIES, AND REACTIONS OF MONOSULFONATED TRIPHENYLPHOSPHINE (PPH(2)(M-C6H4SO3K) EQUALS TPPMS) COMPLEXES OF IRIDIUM(I) - CRYSTAL AND MOLECULAR-STRUCTURE OF (C2H5)(3)(-C6H4SO3)(-)]CENTER-DOT-H2O()][PPH(2)(M)

Iridium complexes containing the TPPMS ligand (TPPMS = PPh(2)(m-C6H4SO 3K)) have been prepared and studied in DMSO and H2O as a comparison to the PPh(3) analogues in toluene. Measurements of the pH of the comple xes show that most are almost neutral, but Ir(CO)(H)(TPPMS)(3) is basi c (pH 10.7). The basicity of Ir(CO)(H)(TPPMS)(3) is confirmed by its r eaction with H2O to give Ir(CO)(H)(2)(TPPMS)(3)(+). In aqueous solutio n, reaction of trans-Ir(CO)(OH)(TPPMS)2 with H-2 produces only fac-Ir( CO)(H)(3)(TPPMS)(2) not the usual mixture of facial and meridional iso mers. This is attributed to a hydrogen-bonding interaction between the two cis-TPPMS ligands in H2O. Reaction of trans-Ir(CO)(Cl)(TPPMS)(2) with CO in water produces [Ir(CO)(2)(TPPMS)(2)(+)]Cl- and [Ir(CO)(3)(T PPMS)(2)(+)]Cl sequentially in a reaction that is pH dependent. Reacti on of trans-Ir(CO)(OH)(TPPMS)2 with CO results in products based on th e water gas shift-reaction. These complexes of TPPMS are spectroscopic ally very similar to the PPh(3) analogues, but display significantly d ifferent reactions in H2O.