Reactions of Ir(CO)(H)(P(p-tolyl)3)3 with SO2 and O2 Mixtures and with H2SO4, Formation of a Sulfate-Bridged Dimer, and Crystal and Molecular Structure of Ir(CO)(H)(SO2)(P(p-tolyl)3)2

Reactions of HIr(CO)(P( p -tolyl) 3 ) 3 with SO 2, O 2, mixtures of SO 2 and O 2, and H 2 SO 4 are described. Reactions with mixtures of SO 2 /O 2 and with H 2 SO 4 lead to a common product, Ir 2 H 4 (μ-SO 4 )(P( p -tolyl) 3 ) 6, where a bidentate SO 4 2 - bridges the iridium centers. The complex HIr(CO)(P( p -tolyl) 3 ) 3 is stable toward O 2 but reacts readily with SO 2 to give HIr(CO)(SO 2 )(P( p -tolyl) 3 ) 2, which was characterized by a crystal structure determination. The species Ir(CO)(H)(SO 2 )(P( p -tolyl) 3 ) 2 crystallizes in the centrosymmetric triclinic space group P 1̄ with a = 10.675(1) Å, b = 10.882(1) Å, c = 17.740(2) Å, α = 84.626(10)°, β = 83.432(10)°, γ = 87.043(10)°, V = 2036.6(3) Å 3, and Z = 2. Diffraction data (Mo Kα, 2θ = 4.5−45.0°) were collected on a Siemens R3m/V diffractometer, and the structure was refined to R = 3.00% for 4218 independent reflections with F o > 6σ( F o ). The five-coordinate iridium(I) center has a distorted environment (closer to trigonal bipyramidal than to square pyramidal) with H(1)−Ir(1)−S(1) = 171.4(23)°. Bond lengths are Ir−P = 2.303(2) and 2.320(2) Å, Ir−SO 2 = 2.372(2) Å, Ir−CO = 1.906(8) Å, and Ir−H = 1.65(7) Å. The SO 2 ligand has bond distances of S(1)−O(1) = 1.442(7) and S(1)−O(2) = 1.441(7) Å, with O(1)−S(1)−O(2) = 113.1(4)°.