Reactivity of dinuclear ruthenium complex containing two 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligands toward HC≡CCH(OH)(CH3)2

详细

The reaction of (p-cymene)Ru₂(μ-S₂)(S₂C₂B₁₀H₁₀)₂ (I) with HC≡CCH(OH)(CH₃)₂ in dichloromethane led to addition complexes, (p-cymene)Ru₂(μ-S₂)(S₂C₂B₁₀H₁₀)₂(R₁C=CR₂) (R₁ = H, R₂ = C(OH)(CH₃)₂ (II); R₁ = C(OH)(CH₃)₂, R₂ = H (III)). In boiling chloroform both complexes II and III spontaneously lose water to generate two geometrical isomers (p-cymene)Ru₂(μ-S₂)(S₂C₂B₁₀H₁₀)₂(R₁C=CR₂) (R₁ = H, R₂ = C(CH₃)=CH₂ (IV); R₁ = C(CH₃)=CH₂, R₂ = H (V)), respectively. Complexes IV and V could be interconverted in boiling toluene. All these complexes were characterized by elemental analysis, mass spectrometry, and NMR spectroscopy. The molecular structure of complex IV has been determined by X-ray crystallography (CIF file CCDC no. 1443964). Complex IV crystallizes in monoclinic system, space group P2₁/c with a = 10.3717(9), b = 20.3982(17), c = 18.6428(13) Å, β = 111.096(4)°, C₁₉H₄₀B₂₀Ru₂S₆, M_r = 879.27, V = 3679.8(5) ų, ρ_c = 1.587 g/cm³, Z = 4, F(000) = 1752, μ(MoK_α) = 1.179 mm^–1, R = 0.0416 and wR = 0.0848 for 4602 observed reflections (I > 2σ(I)).