Osmium(IV) binuclear nonelectrolytic oxo-bridged carboxylates. Molecular structure of [Os2IV(μ-O)(μ-O2CCCl 3)2Cl4(PPh3)2] ·CH2Cl2

Article abstract of DOI:10.1023/B:RUCO.0000022801.63892.43

The reactions between trans-[Os^VIO₂Cl ₂L₂] (L = PPh₃, AsPh₃, SbPh ₃) and carboxylic acids RCO₂H (R = CH₃, C(CH₃)₃, CH₂Cl, CCl₃, CF ₃) are studied. The resulting binuclear compounds were found to have the general formula [Os₂^IV(μ-O)(μ-O ₂CR)₂Cl₄(L)₂] (L = PPh₃; R = CH₃, C(CH₃)₃, CH₂Cl, CCl ₃, CF₃, and L = AsPh₃; R = CH₃, CH₂Cl, CCl₃, CF₃). X-ray diffraction analysis revealed that the [Os₂^IV(μ-O)(μ-O ₂CCCl₃)₂Cl₄(PPh₃) ₂]·CH₂Cl₂ complex crystallizes in a triclnic system with space group P1 ; a = 10.747(2) A, b = 19.291(4) A, c = 24.614(5) A, α = 100.08(3)°, β = 90.63(3)°, γ = 97.05(3)°, V = 4983.5(17) A³, Z = 4. The Os(μ-O)Os angle is 142.2(7)°. The interaction of trans-[Os ^VIO₂Cl₂(SbPh₃)₂] with all the acids under study is attended by intramolecular redox reaction resulting in SbCl₂Ph₃.