Nitrosyl induces phosphorous-acid dissociation in ruthenium(II)

Autor(es)

Truzzi, Daniela Ramos ^[1] ; Ferreira, Antonio Gilberto ^[2] ; da Silva, Sebastiao Claudino ^[3] ; Castellano, Eduardo Ernesto ^[4] ; Alves Lima, Francisco das Chagas ^[5] ; Franco, Douglas Wagner ^[1]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Inst Quim Sao Carlos, Dept Quim & Fis Mol, Sao Paulo - Brazil

^[2] Univ Fed Sao Carlos, Dept Quim, Sao Paulo - Brazil

^[3] Univ Fed Mato Grosso, Dept Quim, Cuiaba, Mato Grosso - Brazil

^[4] Univ Sao Paulo, Inst Fis Sao Carlos, Dept Fis & Informat, Sao Paulo - Brazil

^[5] Univ Estadual Piaui, Ctr Ciencias Nat, Teresina, Piaui - Brazil

• Tipo de documento: Artigo Científico
• Fonte: DALTON TRANSACTIONS; v. 40, n. 48, p. 12917-12925, 2011.
• Citações Web of Science: 9

Resumo

The trans-[Ru(NO)(NH3)(4)(P(OH)(3))]Cl-3 complex was synthesized by reacting [Ru(H2O)(NH3)(5)](2+) with H3PO3 and characterized by spectroscopic (P-31-NMR, delta = 68 ppm) and spectrophotometric techniques (lambda = 525 nm, epsilon = 20 L mol(-1) cm(-1); lambda = 319 nm, epsilon = 773 L mol(-1) cm(-1); lambda = 241 nm, epsilon = 1385 L mol(-1) cm(-1); v(NO+) = 1879 cm(-1)). A pK(a) of 0.74 was determined from infrared measurements as a function of pH for the reaction: trans-[Ru(NO)(NH3)(4)(P(OH)(3))](3+) + H2O (SIC) trans-[Ru(NO)(NH3)(4)(P(O-)(OH)(2))](2+) + H3O+. According to P-31-NMR, IR, UV-vis, cyclic voltammetry and ab initio calculation data, upon deprotonation, trans-[Ru(NO)(NH3)(4)(P(OH)(3))](3+) yields the O-bonded linkage isomer trans-[Ru(NO)(NH3)(4)(OP(OH)(2))](2+), then the trans-[Ru(NO)(NH3)(4)(OP(H)(OH)(2))](3+) decays to give the final products H3PO3 and trans-[Ru(NO)(NH3) (4)(H2O)](3+). The dissociation of phosphorous acid from the [Ru(NO)(NH3)(4)](3+) moiety is pH dependent (k(obs) = 2.1 x 10(4) s(1) at pH 3.0, 25 degrees C). (AU)

• Processo FAPESP: 08/02014-0 - Ataque nucleofílico de íons OH- a complexos trans-[Ru(NO)(NH3)4P(III)]X3, P(III)=P(O)(H)(OEt)2 e P(OtBut)3
• Beneficiário: Daniela Ramos Truzzi
• Modalidade de apoio: Bolsas no Brasil - Mestrado