Synthesis and Reactivity of Hybrid Phosphido- and Hydrosulfido-Bridged Diruthenium Complexes: Transformations into Diruthenium and Tetraruthenium Complexes Bridged by Phosphido and Sulfido Ligands

The reaction of the monophosphido-bridged diruthenium­(III) complex [Cp*RuCl­(μ-PMe2)­(μ-Cl)­RuClCp*] with sodium hydrogen sulfide affords the hybrid phosphido- and hydrosulfido-bridged diruthenium­(III) complex [Cp*RuCl­(μ-PMe2)­(μ-SH)­RuClCp*]. The hydrosulfido-bridged diruthenium­(III) complex can be further converted into the corresponding sulfido-bridged multinuclear ruthenium­(III) complex via deprotonation of the hydrosulfido ligand. The hydrosulfido-bridged diruthenium­(III) complex also reacts with bases to afford a coordinatively unsaturated diruthenium­(III) complex, where insertion of terminal alkynes further occurs to form phosphido-bridged diruthenium­(III) complexes bearing ruthenathiacyclobutene moieties.