Issue 48, 2011
From the journal:

Dalton Transactions

Nitrosyl induces phosphorous-acid dissociation in ruthenium(ii)†

Daniela Ramos Truzzi,a   Antonio Gilberto Ferreira,b   Sebastião Claudino da Silva,c   Eduardo Ernesto Castellano,d   Francisco das Chagas Alves Limae  and  Douglas Wagner Franco*a  

* Corresponding authors

a Departamento de Química e Física Molecular, Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador São-carlense, 400, Centro, São Carlos, São Paulo, Brazil
E-mail: douglas@iqsc.usp.br
Fax: 55-16-3373-9976
Tel: 55-16-3373-9976

b Departamento de Química, Universidade Federal de São Carlos, Rodovia Washington Luiz, km 235, São Carlos, São Paulo, Brazil

c Departamento de Química, Universidade Federal do Mato Grosso, Av. Fernando Correia da Costa, 2367, Boa Esperança, Cuiabá, Mato Grosso, Brazil

d Departamento de Física e Informática, Instituto de Física de São Carlo, Universidade de São Paulo, Av. Trabalhador São-carlense, 400, Centro, São Carlos, São Paulo, Brazil

e Centro de Ciências da Natureza, Coordenação de Química, Universidade Estadual do Piauí, Rua João Cabral, Teresina, Piauí, Brazil

Abstract

The trans-[Ru(NO)(NH3)4(P(OH)3)]Cl3 complex was synthesized by reacting [Ru(H2O)(NH3)5]2+ with H3PO3 and characterized by spectroscopic (31P-NMR, δ = 68 ppm) and spectrophotometric techniques (λ = 525 nm, ε = 20 L mol−1 cm−1; λ = 319 nm, ε = 773 L mol−1 cm−1; λ = 241 nm, ε = 1385 L mol−1 cm−1; νNO+ = 1879 cm−1). A pKa 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 ⇌ trans-[Ru(NO)(NH3)4(P(O−)(OH)2)]2+ + H3O+. According to 31P-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 (kobs = 2.1 × 10−4 s−1 at pH 3.0, 25 °C).

Graphical abstract: Nitrosyl induces phosphorous-acid dissociation in ruthenium(ii)

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Article information

DOI
https://doi.org/10.1039/C1DT10936G
Article type
Paper
Submitted
18 May 2011
Accepted
03 Sep 2011
First published
25 Oct 2011

Dalton Trans., 2011,40, 12917-12925

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Nitrosyl induces phosphorous-acid dissociation in ruthenium(II)

D. R. Truzzi, A. G. Ferreira, S. C. da Silva, E. E. Castellano, F. D. Chagas Alves Lima and D. W. Franco, Dalton Trans., 2011, 40, 12917 DOI: 10.1039/C1DT10936G

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