Synthesis and Characterization of New Ammine Ru(II) Complexes Containing P(m-tol)3, P(p-CH3)3 and P(OC5H11)3

• Autor(a) principal: Signini,Roberta
• Data de Publicação: 2002
• Outros Autores: Mazzetto,Selma E.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Journal of the Brazilian Chemical Society (Online)
• Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532002000500017
• topic: ruthenium(II); ammine complexes; phosphine; phosphite ligands

Direct reactions between [Ru(NH3)5(H2O)](PF6) 2 (1) and P(m-tol)3 (a), P(p-tol)3 (b) and P(OC5H11)3 (c) lead the complexes [Ru(NH3)5P(m-tol)3](PF 6)2 (2a), trans-[Ru(NH3)4{P(p -tol)3}2](PF6)2 (3b) and trans-[Ru(NH3)4{P(OC5H 11)3}2](PF6)2 (3c) respectively. These complexes have been isolated as hexafluorophosphate salts and characterized by elemental analysis, cyclic voltammetry and UV-VIS spectra measurements. One ammonia ligand in 2a is displaced at the a specific rate of 4.3 x 10-3 s-1 (25 ºC, μ = 0.10 mol L-1). The aquo species trans-[Ru(NH3)4(L)H2O]2+ (L = P(p-tol)3, 4b; L = P(OC5H11)3, 4c) are generated by the substitution of one L ligand with H2O, from trans-[Ru(NH3)4(L)2]2+ with k-1 = 2.7 x 10-3 s-1 [L = P(p-tol)3, 3b] and 3.5 x 10-3 s-1 [L = P(OC5H11)3 3c] (25 ºC, μ = 0.10 mol L-1) (NaCF3COO/CF3COOH; C H+ = 1.0 x 10-3 mol L-1). The formal reduction potentials for the species 3b, 3c and 2a are 0.50 ± 0.01V, 0.48 ± 0.01V and 0.50 ± 0.02V, respectively (vs SCE) [μ = 0.10 mol L-1 ; NaCF3COO; C H+ = 1.0 x 10-3 CF3COOH]. The following reactions: <IMG SRC="http:/img/fbpe/jbchs/v13n5/12819x2.gif"> [L = P(m-tol)3, P(p-tol)3 and P(OC5H11)3] were studied and the calculated values for k1, k-1 and Keq are 0.28 mol-1 L s-1, 0.06 s-1, 4.67 mol-1 L [L = P(m-tol)3, 4a]; 0.25 mol-1 L s-1, 0.04 s-1, 6.25 mol-1 L [L = P(p-tol)3, 4b]; 12.4 mol-1 L s-1, 5.8x10-1 s-1, and 21 mol-1 L [L = P(OC5H11)3, 4c], [25.0 ± 0.2 ºC; m = 0.10 mol L-1; NaCF3COO; C H+ = 1.0 x 10-3 CF3COOH].