A convenient route to an uncommon class of polymeric and binuclear ruthenium(I) complexes containing diphosphine and dithioether ligands

Article abstract of DOI:10.1021/om00097a037

Reaction of either the carboxylate-bridged dimers [Ru(CO)₂(μ-O₂CR)(NCMe)]₂ or the polymeric dimers [Ru₂(CO)₄(μ-O₂CR)₂]_n (R = Me, Et) with 1 equiv (per dimer unit) of the bidentate groups L₂ (L₂ = R′₂PCH₂PR′₂, R′ = Ph (DPPM), Me (DMPM); L₂ = R′SCH₂SR′, R′ = Ph, Me) yields the unusual Ru(I) polymers [Ru₂(CO)₄(μ-O₂CR)₂(L ₂)]_n, in which two metals are bridged by two carboxylate groups and these binuclear units are linked by diphosphine or dithioether ligands. Reaction with 2 equiv of the diphosphine Ph₂PCH₂PPh₂ in THF yields the neutral disubstituted dimer [Ru₂(CO)₄(μ-O₂CMe)₂(η ¹-DPPM)₂], whereas with DPPM or Ph₂P(CH₂)₂PPh₂ (DPPE) in alcohols two types of cationic compounds of formula [Ru₂(CO)₄(μ-O₂CMe)(L₂) ₂]⁺ (L₂ = DPPM, DPPE) are obtained. The X-ray structures of both cationic species have been determined and show that one has the Ru(I) centers bridged by two DPPM and one acetate ligand, whereas the other has two bridging carbonyls and one bridging acetate group, with one DPPE chelating each metal.