108294-67-3Relevant academic research and scientific papers
Polymeric ruthenium(I) and binuclear ruthenium(I) and osmium(I) carboxylate-bridged complexes containing diphosphine, diarsine, arsinophosphine, diphosphine chalcogenide, and dithioether ligands: The structure of [Ru2(CO)4(μ-O2CMe)2(MeSCH 2SMe)]2·THF
Hilts, Robert W.,Sherlock, Stephen J.,Cowie, Martin,Singleton, Eric,De Steyn, Margot M. V.
, p. 3161 - 3167 (2008/10/08)
The addition of 1 molar equiv of the bidentate ligands L L, R′2P(CH2)nPR′2, R′2As(CH2)nAsR′2, Ph2P(CH2)2AsPh2, Ph2PCH2P(S)Ph2, Ph2P(S)CH2P(S)Ph2, and R′SCH2SR′ (R′ = Me, Ph; n = 1-4), to THF/acetone solutions of either the polymer [Ru2(CO)4(μ-O2CMe)2]n or the dimers [Ru2(CO)4(μ-O2CR)2(NCMe) 2] (R = Me, Et) affords a new class of polymeric species, [Ru2(CO)4(μ-O2CR′)2(L L)]n, in which the carboxylate-bridged dimeric units are linked by the bidentate L L ligands. The use of 2 molar equiv of either Ph2PCH2PPh2 (dppm) or Ph2PCH2P(S)Ph2 (dppmS) in the reaction with the acetate-bridged dimer yields complexes of the type [Ru2(CO)4(μ-O2CMe)2(η 1-Ph2PCH2P(X)Ph2)2] (X = S, electron pair). The osmium analogues [Os2(CO)4(μ-O2CMe)2(η 1-Ph2PCH2P(X)Ph2)2] can be obtained by heating [Os2(CO)6(μ-O2CMe)2] with 2 equiv of dppm or dppmS in CHCl3. The pendant PPh2 moieties of [Os2(CO)4(μ-O2CMe)2(η 1-dppm)2] can be oxidized to P(O)Ph2 groups by treatment with 2 molar equiv of H2O2. The structure of the dithioether species [Ru2(CO)4(μ-O2CMe)2(MeSCH 2SMe)]2·THF has been determined by an X-ray diffraction study and has been shown to consist of a polymeric chain of [Ru2(CO)4(μ-O2CMe)2] units linked by MeSCH2SMe ligands. Each dimer unit has a sawhorse-like arrangement in which the four carbonyls are opposite the bridging acetate groups. The independent Ru-Ru bonds are 2.682 (1) and 2.684 (1) A?. This compound crystallizes in the space group P1 with a = 15.838 (2) A?, b = 17.562 (2) A?, c = 8.238 (2) A?, α = 102.55 (1)°, β = 101.87 (1)°, γ = 68.17 (1)°, V = 2056.3 A?3, and Z = 2. The asymmetric unit contains two [Ru2(CO)4(μ-O2CMe)2(MeSCH 2SMe)] moieties. On the basis of 3533 unique observations and 435 parameters varied, the structure was refined to R = 0.046 and Rw = 0.055.
A convenient route to an uncommon class of polymeric and binuclear ruthenium(I) complexes containing diphosphine and dithioether ligands
Sherlock, Stephen J.,Cowie, Martin,Singleton, Eric,De V. Steyn, Margot M.
, p. 1663 - 1666 (2008/10/08)
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.
