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(MU-O2CME)2(MESCH2SME)]2.THF

The addition of 1 molar equiv of the bidentate ligands [formula omited], 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[formula omited]n, in which the carboxylate-bridged dimeric units are linked by the bidentate [formula omited] 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(η1-Ph2PCH2P(X)Ph2)2] (X = S, electron pair). The osmium analogues [Os2(CO)4(μ-O2CMe)2(η1-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(η1-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(MeSCH2SMe)]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) Å. This compound crystallizes in the space group [formula omited] with a = 15.838 (2) Å, b = 17.562 (2) Å, c = 8.238 (2) Å, α = 102.55 (1)°, β = 101.87 (1)°, γ = 68.17 (1)°, V = 2056.3 Å3, and Z = 2. The asymmetric unit contains two [Ru2(CO)4(μ-O2CMe)2(MeSCH2SMe)] moieties. On the basis of 3533 unique observations and 435 parameters varied, the structure was refined to R = 0.046 and Rw = 0.055. © 1990, American Chemical Society. All rights reserved.