Room temperature ring opening of a 1,3-dithiole-2-thione at a dimolybdenum centre

The reaction of [Mo-2(CO)(4)Cp-2] (1; CP=eta-C5H5) with 4,5-bis(carbomethoxy)-1, 3-dithiole-2-thione at room temperature affords two products, both of which have been crystallographically characterised. In the first, [Mo-2{mu-SCS2C2(CO2Me)(2)} (CO)(5)Cp-2] (2), the Moequivalent toMo bond has been completely cleaved and the complex consists of the heterocycle eta(2)-side-bound through the thione function to a CpMo(CO)(2) unit, with an additional CpMo(CO)(3) group attached to the thione sulfur atom. In the second complex, [Mo-2{mu-SCSC(CO2Me)=C(CO2Me)S}(CO)(3)Cp-2](3) the Mo-Mo bond has been retained and partial ring opening of the heterocycle by C-S bond cleavage has occurred, the latter being bonded as a thiolate ligand to one molybdenum and through the thione group to both metals. (C) 2003 Elsevier Science B.V. All rights reserved.