Insertion of SO₂ into the S−S Bond of Cp₂MoS₂ and Cp₂MoS₂O To Give Molybdocene Dithiosulfate and Bis(<i>O</i>-alkylthiosulfates)

Cp2MoS2, 3, reacts with SO2 in CH2Cl2/EtOH mixtures to give Cp2MoS3O2, 4, wherein the SO2 has inserted into the S−S bond to give a dithiosulfate ligand. Crystal data for 4: P21/n, a = 7.6782(6) Å, b = 14.580(3) Å, c = 10.2730(10) Å, β = 92.04(1)°, V = 1149(3) Å3, Z = 4. Cp2MoS2O, 5, reacts with SO2 in CH2Cl2 to give low yields of 4 plus other identified products. 5 reacts with SO2 in MeOH and EtOH to give the corresponding bis(O-alkylthiosulfate), 6a and 6b, respectively. Crystal data for 6a: P1̄, a = 8.3226(13) Å, b = 8.4736(11) Å, c = 12.382(2) Å, α = 87.803(11)°, β = 77.758(11)°, γ = 86.383(12)°, V = 851.4(2) Å3, Z = 2.