Synthesis, characterization and structure of ruthenium(II) phosphine complexes with N-heterocyclic thiolate ligands

• Published in: Inorganica Chimica Acta 2006-01, Vol.359 (2), p.391-400
• Main Authors: Pinheiro, Solange O., de Sousa, Jackson R., Santiago, Marcelo O., Carvalho, Idalina M.M., Silva, Ana L.R., Batista, Alzir A., Castellano, Eduardo E., Ellena, Javier, Moreira, Ícaro S., Diógenes, Izaura C.N.
• Format: Article
• Language: English
• Subjects: Chemically modified electrode; Cyt c; N-Heterocyclic thiolate ligands; Ruthenium phosphine compounds; SAM; SERS
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2005.05.042

The structural characterizations show that, during the reaction of the mer-[RuCl 3(dppb)(OH 2)] complex with the 2,2′-dithiobis(benzothiazole) ligand, the S–S bond of this molecule is cleaved thus forming two four-membered chelate rings coordinated to the ruthenium through the N,S-donor atoms of the 2-mercaptobenzothiazole reduced ligand, with an average bite angle of 67.295(11)°. The [Ru(dppb)(mbt) 2], mbt = 2-mercaptobenzothiazole, complex, isolated from the reaction of the mer-[RuCl 3(dppb)(OH 2)] complex with the 2,2′-dithiobis(benzothiazole), mbts, was characterized by spectroscopic and electrochemical techniques ( E 1/2 = 0.78 V versus NHE) and its structure was determined by crystal X-ray analysis. The structural analysis suggests that the S–S bond of the mbts ligand is cleaved, thus forming two four-membered chelate rings coordinated to the ruthenium through the N,S-donor atoms of the mbt reduced ligands, with an average bite angle of 67.295(11)°. The 1H and 13C NMR signals observed for mbts ligand coordinated to the metal center, the changes in the vibrational spectra, and the appearance of a MLCT band in the electronic spectrum of the complex point for the reduced state of the ruthenium metal center, Ru II. These reducing processes are suggested to be due to the methanol interference, which is observed to be strongly affected by N-methylmorpholine. The cytochrome c electrochemistry was analyzed by using the SAMs formed by the mbts and the [Ru(dppb)(mbt) 2] complex on gold, with only the former presenting electroactivity.