The X-ray crystal structure and reactivity of trans-[RuCl 2(P(OC 2H 5) 3) 4]

• Published in: Polyhedron 1999-01, Vol.18 (7), p.979-983
• Main Authors: Mazzetto, Selma Elaine, Gambardella, Maria Teresa do Prado, Santos, Regina Helena Almeida, Lopes, Luiz Gonzaga de França, Franco, Douglas Wagner
• Format: Article
• Language: English
• Subjects: Reactivity; Structure; trans-[RuCl 2(P(OC 2H 5) 3) 4]
• ISSN: 0277-5387
• DOI: 10.1016/S0277-5387(98)00382-9

The X-ray structure of trans-[RuCl 2(P(OC 2H 5) 3) 4] indicates that the molecule has the C 2 symmetry with the Ru(II) and the two Cl ions lying on the two-fold axis. The E Ru(III)/Ru(II) O′ in the trans-[RuCl 2(P(OC 2H 5) 3) 4] complex is 0.61±0.01 vs. SCE, ( μ=0.10 M NaCF 3COO/CF 3COOH, ethanol/water 2:1, 25°C, C H +=1.0×10 −2 M). In the same experimental conditions the electronic spectrum of this complex exhibit two bands: 254 nm ( ε≅6.7×10 3 M −1 cm −1) and 410 nm ( ε=8×10 M −1 cm −1) and a shoulder at 290 nm ( ε≅6×10 2 M −1 cm −1). Only one signal (128 ppm) is observed in the 31P NMR spectrum of trans-[RuCl 2(P(OC 2H 5) 3) 4] in ethanol (130 ppm) or ethanol/water buffered solutions at pH=7.0 (128 ppm). In ethanol or ethanol/water buffered solutions, the complex trans-[RuCl 2(P(OC 2H 5) 3] 4, exhibits dissociation of two chloride ligands ( k −Cl − =(3.2±0.2)×10 −5 s −1; 25°C, μ=0.10 (NaCF 3COO), yielding as a product the [Ru(P(OC 2H 5) 3) 4S 2] 2+ ion in which the two axial positions are occupied by solvent molecules (S). In the presence of acid, the final product is the cis-[Ru(P(OC 2H 5) 3) 2S 4] 2+ ion.