Cationic iridium(I) complexes as catalysts for the alcoholysis of silanes

The syntheses of five cationic iridium(l) complexes, containing the bidentate ligands bis-(1-pyrazolyl)methane (BPM) and bis(3,5-dimethyl-1-pyrazolyl)methane (dmBPM), {[Ir(BPM)-(COD)](+)(BPh4)(-)} (1), {[Ir(dmBPM)(COD)](+)(BPh4)(-)} (2), {[Ir(BPM)(COD)](+)[Ir(COD)Cl-2](-)} (4), {[Ir(BPM)(CO)(2)](+)(BPh4)(-)} (3), and {[Ir(dmBPM)(CO)(2)](+)(BPh4)(-)} (5), are reported. The complexes were characterized by NMR spectroscopy, and the solid-state structure of {[Ir(BPM)(CO)(2)](+)(BPh4)(-)} (3) was determined by single-crystal X-ray crystallographic analysis. The complexes {[Ir(BPM)(CO)(2)](+)(BPh4)(-)} (3) and {[Ir(dmBPM)(CO)(2)](+)(BPh4)(-)} (5) are effective catalysts for the alcoholysis of a range of alcohols and hydrosilanes, including secondary and tertiary hydrosilanes, under mild conditions.