Synthesis and Characterization of New Ammine Ru(II) Complexes Containing P(m-tol)3, P(p-CH3)3 and P(OC5H11)3
Document title: Synthesis and Characterization of New Ammine Ru(II) Complexes Containing P(m-tol)3, P(p-CH3)3 and P(OC5H11)3
Journal: Journal of the Brazilian Chemical Society
Database: PERIÓDICA
System number: 000311157
ISSN: 0103-5053
Authors: 1
2
Institutions: 1Universidade de Sao Paulo, Instituto de Quimica de Sao Carlos, Sao Carlos, Sao Paulo. Brasil
2Universidade Federal do Ceara, Departamento de Quimica Organica e Inorganica, Fortaleza, Ceara. Brasil
Year:
Season: Sep
Volumen: 13
Number: 5
Pages: 647-652
Country: Brasil
Language: Inglés
Document type: Artículo
Approach: Experimental, aplicado
English abstract 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; CH+ = 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; CH+ = 1.0 x 10-3 CF3COOH]. The following reactions: [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; CH+ = 1.0 x 10-3 CF3COOH]
Portuguese abstract As reações diretas entre [Ru(NH3)5(H2O)](PF6) 2 (1) e P(m-tol)3 (a), P(p-tol)3 (b) e P(OC5H11)3 (c) forneceram os complexos [Ru(NH3)5P(m-tol)3](PF 6)2 (2a), trans-[Ru(NH3)4{P(p- tol)3}2](PF6)2 (3b) e trans-[Ru(NH3)4{P(OC5H 11)3}2](PF6)2 (3c), respectivamente. A constante de velocidade específica de substituição da amônia em (2a) foi de 4,3 x 10-3 s-1 (25 oC, μ = 0,10 mol L-1). Os aquo complexos trans-[Ru(NH3)4(L)(H2O)] 2+ (L = P(p-tol)3, 4b; L = P(OC5H11)3, 4c) foram gerados pela aquação térmica de uma das moléculas de L, dos respectivos complexos trans-[Ru(NH3)4L2 ]2+ (L = P(p-tol)3, 3b; L = P(OC5H11)3, 3c) e os valores das constantes foram: k-1 = 2,7 x 10-3 s-1 e k-1 = 3,5 x 10-3 s-1, respectivamente. Os valores dos potenciais formais de redução para 3b, 3c e 2a foram 0,50 ± 0,01V; 0,48 ± 0,01V e 0,50 ± 0,02V, respectivamente (vs SCE) [μ = 0,10 mol L-1; NaCF3COO; CH+ = 1,0 x 10-3 CF3COOH]. As reações: foram estudadas e os valores de k1, k-1 e Keq foram 0,28 mol-1 L s-1, 0,06 s-1, 4,67 mol-1 L [para L = P(m-tol)3, 4a]; 0,25 mol-1 L s-1, 0,04 s-1, 6,25 mol-1 L [para L = P(p-tol)3, 4b] e 12,4 mol-1 L s-1, 5,8 x 10-1 s-1, 21 mol-1 L [para L = P(OC5H11)3, 4c] [25oC; μ = 0,10 mol L-1; NaCF3COO; CH+ = 1,0 x 10-3 CF3COOH]
Disciplines: Química
Keyword: Química organometálica,
Rutenio,
Aminas,
Fosfinas,
Ligandos de fosfito
Keyword: Chemistry,
Organometallic chemistry,
Ruthenium,
Amines,
Phosphines,
Phosphite ligands
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