Abstract

The reaction of [Mo 2(CO) 4Cp 2] ( 1; Cp=η-C 5H 5) 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{μ-SCS 2C 2(CO 2Me) 2}(CO) 5Cp 2] ( 2), the Mo≡Mo bond has been completely cleaved and the complex consists of the heterocycle η 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{μ-SCSC(CO 2Me)C(CO 2Me)S}(CO) 3Cp 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.

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