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Type: Artigo de periódico
Title: 4,4 '-dithiodipyridine as a bridging ligand in osmium and ruthenium complexes: The electron conductor ability of the -S-S- bridge
Author: Silva, WC
Lima, JB
Moreira, IS
Neto, AM
Gandra, FCG
Ferreira, AG
McGarvey, BR
Franco, DW
Abstract: The compounds [Ru(NH(3))(5)(dtdp)](TFMS)(3), [Os(NH(3))(5)(dtdp)](TFMS)(3), [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](TFMS)(6), [(NH(3))(5)Os-(dtdp)Ru(NH(3))(5)](TFMS)(3)(PF(6))(2), and [(NH(3))(5)Os(dtdp)Fe(CN)(5)] (dtdp = 4,4'-dithiodipyridine, TFMS = trifluoromethane-sulfonate) have been synthesized and characterized by elemental analysis, cyclic voltammetry, electronic, vibrational, EPR, and (1)H NMR spectroscopies. Changes in the electronic and voltammetric spectra of the ion complex [Os-(NH(3))(5)(dtdp)](3+) as a function of the solution pH enable us to calculate the pK(a) for the [Os(NH(3))(5)(dtdpH)](4+) and [Os(NH(3))(5)(dtdpH)](3+) acids as 3.5 and 5.5, respectively. The comparison of the above pK(a) data with that for the free ligand (pK(1) = 4.8) provides evidence for the -S-S- bridge efficiency as an electron conductor between the two pyridine rings. The symmetric complex, [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](6+), is found to exist in two geometric forms, and the most abundant form (most probably trans) has a strong conductivity through the -S-S- bridge, as is shown by EPR, which finds it to have an S = 1 spin state with a spin-spin interaction parameter of 150-200 G both in the solid sate and in frozen solution. Further the NMR of the same complex shows a large displacement of unpaired spin into the pi orbitals of the dftp ligand relative to that found in [Os(NH(3))(5)(dtdp)](3+). The comproportionation constant, K(c) = 2.0 x 10(5), for the equilibrium equation [Os(II)Os(II)] + [Os(III)Os(III)] reversible arrow 2[Os(II)Os(III)] and the near-infrared band energy for the mixed-valence species (MMCT), [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](5+) (lambda(MMCT) = 1665 nm, epsilon = 3.5 x 10(3) M(-1) cm(-1), Delta(nu) over bar (1/2) = 3.7 x 10(3) cm(-1), alpha = 0.13, and H(AB) = 7.8 x 10(2) cm(-1)), are quite indicative of strong electron delocalization between the two osmium centers. The electrochemical and spectroscopic data for the unsymmetrical binuclear complexes [(NH(3))(5)Os(III)(dtdp)Ru(II)(NH(3))(5)](5+) (lambda(MMCT) = 965 nm, epsilon = 2.2 x 10(2) M(-1) cm(-1), Delta(nu) over bar (1/2) = 3.0 x 10(3) cm(-1), and H(AB) = 2.2 x 10(2) cm(-1)) and [(NH(3))(5)Os(III)(dtdp)Fe(II)(CN)(5)] (lambda(MMCT) = 790 nm, epsilon = 7.5 x 10 M(-1) cm(-1), Delta(nu) over bar (1/2) = 5.4 X 103 cm(-1), and HAB = 2.0 x 102 cm(-1)) also suggest a considerable electron delocalization through the S-S bridge. As indicated by a comparison of K, and energy of the MMCT process in the iron, ruthenium, and osmium complexes, the electron delocalization between the two metal centers increases in the following order: Fe < Ru < Os.
Country: EUA
Editor: Amer Chemical Soc
Rights: fechado
Identifier DOI: 10.1021/ic034630o
Date Issue: 2003
Appears in Collections:Unicamp - Artigos e Outros Documentos

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