The syntheses, structures, and reactivities of *2 2(µ-8)(µ-82)(µ-88•8 2)•8 2, 1•2802, and Cp*2Cr2^-S)^-S2)(M-SS03)'(CD30D)iattice, 2, are reported. Reversible addition of S02 to Cp*2Cr2S5,1, to give 1•2802 was found to occur at room temperature. 1 possesses a novel µ-1-82 ligand, and X-ray crystallography of 1•2802 showed that S02 binds as a Lewis acid to the terminal sulfur of this ligand with an acute S-S-S angle (94°). The S-S02 distance of 2.41 A is about 0.2 A shorter than in the previously known *2 2(µ-8)(µ-82)(µ-8•802). Consistent with this greater activation, 1•2802 further reacts in the presence of excess S02 to give the thiosulfate 2 (isomorphous to the Mo analogue) at a much faster rate than in the Mo system. Significantly, the crystal structure of 1•2802 shows the presence of associated S02 molecules unsymmetrically bridging (via sulfur) the oxygen atoms of each sulfidebound S02 molecule to give a cyclic aggregate of four S02 molecules (intermolecular S-O distances of 2.78 and 2.95 A). Infrared studies demonstrate that these interactions further activate (weaken) the 8=0 bonds of the sulfide-bound S02. Thus, it is proposed that the mechanism of S02 disproportionation in solution involves baseassisted oxygen atom transfer from the sulfide-bound S02 molecule to the associated S02 to produce S03. The S03 then displaces S20 (which decomposes to Sg and S02) from the bridging sulfide ligand to give the observed thiosulfate product. The reactivities of 1•2802 and Cp*2Cr2S,cS02 vs € *2 284•802 and of 2 vs Cp*2Mo2S4'S03 are discussed.A mechanism for the oxygen atom transfer reaction is proposed on the basis of the crystal structure of 1•2802 and 34S-labeling studies. Facile reaction of Cp*2Cr2S4 with Sg was found to give 1, and all five of the core sulfurs in the latter incorporated 34S if excess 34S8 was used. 1•2802 and 2 crystallize in the space groups C2/c and P\, respectively. The cell dimensions are the following: 1•2802, a = 16.087 (4) A, b = 15.926 (3) A, c = 21.650 (3) A, ß = 105.29 (2)°, and Z = 8; 2, a = 10.336 (2) A, b = 10.891 (2) A, c = 13.219 (3) A, a = 85.15 (3)°, ß = 78.85 (3)°, y = 62.39 (3)°, and Z = 2. R = 4.85% for 1-2S02, and R = 4.84% for 2.Cp*2Cr2^-S)(M-S2)(g-SS-S02)-S02,1-2S02, and the "S03 adduct" Cp*2Cr2S4-S03, 2, which importantly now contains one less sulfur and is isostructural with the Mo species discussed above. The crystal structure of 1-2S02 as well as 34S-labeling studies suggest a possible oxygen-transfer mechanism for the conversion of 1*2S02 to 2 in which self-aggregation of SO¡ via weak Lewis acid-base interactions induced by electron donation from sulfide plays a critical role.
Experimental SectionReactions were carried out under inert atmosphere using Schlenk techniques. Reagent grade solvents and S02 were usually used as received, but for some reactions solvents were dried by distillation from appropriate drying agents. 34S was obtained from the Mound Facility of Monsanto Research Corp., Miamisburg, OH. Samples of Cp*2Cr2S4, Cp*2Cr2Ss, and Cp'2W2S4 (Cp' = -BuCp) were g...