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A novel C-S bond formation has been found in the reaction of [{Ru(AN)3(TMP)2}2(/<-S2)]4+ with acetone (AN is acetonitrile, and TMP is P(OMe)3). The crystal structure of the resulting compound, [{Ruln(AN)2(TMP)2}(/<-S2CH2C0CH3){Ruin(AN)3(TMP)2}](CF3S03)30.5(CH3)2C0, has been solved by single-crystal X-ray diffraction analysis. The crystal data are as follows: triclinic, space group PI, a = 12.238(4) k,b = 22.248(7) Á, c = 12.344(4) Á, a = 93.29(3)°, ß = 112.69(2)°, = 78.54(3)°, V = 3074(2) Á3, and Z = 2. The two ruthenium atoms originally bridged by a S22bridging ligand in the starting material are bridged by a S2CH2COCH33ligand in the product with the two sulfur-coordinating atoms. In the new bridging ligand, deprotonated acetone, CH3COCH2-, is bonded to the S22bridge, forming a C-S bond. The carbonyl oxygen atom of the new bridge coordinates to one of the ruthenium atoms to form a RuOCCS five-membered ring. The S-S distance is 2.067-(6) Á, the two Ru-S distances are 2.339(5) and 2.380(5) Á, and the two Ru atoms are attached to the S-S bridging ligand in a fans mode.Multinuclear transition-metal complexes with sulfur-containing bridging ligands have been investigated to mimic the function of nitrogenase enzymes1-7 and to study the hydrodesulfurization of thiophene and other organosulfur compounds in the refinement of fossil fuels.8-15 The latter reactions are usually catalyzed at the surface of transition-metal sulfides. Mechanistic studies of the desulfurization and its reverse reactions in homogeneous solution have been carried out on sulfideand hydrosulfide-bridged multinuclear transition metal complexes by DuBois15-19 and Rauchfuss et al.12-15•20 Sulfide and hydrosulfide ligands exhibit novel C-O cleavage of cyclic ethers, forming a C-S bond;16 they also undergo addition of

Reaction of [{Ru(CH3CN)3[P(OMe)3]2}2(μ-S2)](PF6)3 with a mixture of acetylene and O2 gave a novel ruthenium(IV) dimer complex [{Ru(IV)(PFO3)[P(OMe)3]2}2(μ-S)(μ-PF2O2)2]. The newly formed bridging and terminal ligands PF2O2− and PFO32− are produced from the reaction of PF6− with trace amounts of H2O in the solvent. Although acetylene is not incorporated in the final product, it is necessary to accelerate the reaction. Ruthenium(IV) complexes with S2− ligand are rare and only two examples are previously known. The crystal of [{Ru(PFO3)[P(OMe)3]2}2(μ-S)(μ-PF2O2)2] is monoclinic, space group P21/n, a = 11.061(5), b = 20.764(4), c = 17.074(3) Å, β = 95.74(2)°, V = 3901(1) Å3, and Z = 4. The bridging PF2O2− ligand coordinates to Ru atoms with the two oxygen atoms, while the terminal PFO32− ligand coordinates to a Ru atom with one of the oxygen atoms. The molecular structure is confirmed by 31P and 19F NMR spectroscopy.

The title compound having two hydrazine bridges between the two ruthenium centers has been synthesized, and the structure is compared to that of the previously reported complex with a single hydrazine bridge, [{RuCl(TMP)2}2(μ-Cl)(μ-N2H4)(μ-S2)].

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