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.

单膦桥联二钌(III)配合物[Cp*RuCl(μ-PMe₂)(μ-Cl)RuClCp*]与硫氢化钠发生反应，可生成兼具膦基与氢硫化物基桥联的二钌(III)杂化配合物[Cp*RuCl(μ-PMe₂)(μ-SH)RuClCp*]。该氢硫化物桥联二钌(III)配合物可通过氢硫化物配体的脱质子反应，进一步转化为相应的硫化物桥联多核钌(III)配合物。该氢硫化物桥联二钌(III)配合物还可与碱反应生成配位不饱和二钌(III)配合物，端炔烃可进一步插入该配合物中，形成带有钌硫杂环丁烯结构单元的膦桥联二钌(III)配合物。