235422-10-3Relevant academic research and scientific papers
Some new chain-like terdentate phosphines, their ruthenium(II) coordination chemistry and the activity of the cations [Ru(MeCN)3(PhP{CH2CH2P(p-X-C6H 4)2}2)]2+ (X=H, F, Me and OMe) as acetalization catalysts
Jiang, Qiongzhong,Rueegger, Heinz,Venanzi, Luigi M.
, p. 64 - 79 (1999)
The new chain-like tritertiary phosphines PhP{CH2CH2P(p-X-C6H4) 2}2, (X=F, Me and OMe), phetpX, were prepared and characterized. These ligands react with cis-[RuCl2(DMSO)4] giving equilibrium mixtures of the eclipsed (ec) and staggered (st) isomers of the dinuclear complexes [Ru2(μ-Cl)3(phetpX)2]Cl. The preparation and characterization of the tritertiary phosphines MesP{CH2CH2P(p-X-C6H4) 2}2 (Mes=mesityl, X=H and F), mesetpX, is also reported. They react with cis-[RuCl2(DMSO)4] giving equilibrium mixtures of corresponding uninuclear, [RuCl2(mesetpX)], and dinuclear species, st-[Ru2(μ-Cl)3(mesetpX)2]Cl, whose molecularities were established by determining their diffusion coefficients. The dissociation of st-[Ru2(μ-Cl)3(mesetph)2]Cl to [RuCl2(mesetph)] (K=1.8×10-2 mol-1) is endothermic (ΔH=32 kJ mol-1) and favored by entropy (ΔS=75 J mol-1). The complexes 'RuCl2(pp2)' (pp2=phetph, and mesetph) react with CO giving fac-[RuCl2(CO)(pp2)] and fac-[RuCl(CO)2(pp2)]Cl as kinetic products. These complexes slowly rearrange to the thermodynamically stable products mer-[RuCl2(CO)(pp2)]. The complexes st-[Ru2(μ-Cl)3(phetpX)2]Cl react with four equivalents of AgCF3SO3 in MeCN giving the corresponding salts [Ru(MeCN)3(phetpX)](CF3SO3)2. Their activities as catalysts for the acetalization of cyclo-hexanone with 1,2-dihydroxyethane and the trans-acetalization of cyclo-hexanone with 2,2-dimethyl-1,3-dioxolane are described.
