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Ru(ii)-dmso complexes containing azole-based ligands: Synthesis, linkage isomerism and catalytic behaviour

The reaction of cis,fac-[RuCl2(dmso-S)3(dmso-O)], 1, with different azole (L) ligands leads to new [RuCl2(L)(dmso-S)3] compounds (L = CH3-pz-H, 2; NO2-pz-H, 3; CF3-pz-H, 4 and Br-Hind, 5). Complexes 2-5 have been characterized by analytical, spectroscopic and electrochemical techniques as well as by monocrystal X-ray diffraction analysis. Upon oxidation to Ru(iii) the complexes undergo linkage isomerization of a S-bound dmso ligand and the corresponding kinetic rates as well as the thermodynamic properties have been determined for compound 2 and also for the previously described [RuIICl2(pypz-H)(dmso-S)2] (pypz-H = 2-(3-pyrazolyl)pyridine), 6, from cyclic voltammetries performed at different scan rates. The exposure of compound 2 to visible light in acetonitrile produces the substitution of one dmso ligand by a solvent molecule generating a new compound, 2′. The irradiation of solutions of compounds 2 and 6 in chloroform leads in both cases to the substitution of one dmso by a chlorido ligand in parallel to the oxidation of Ru(ii) to Ru(iii) generating complexes 2′′ and 6′ respectively. The reactivity of compounds 2-6 has been tested with regard to the hydration of nitriles in water as a solvent, displaying in all cases good performance and selectivity for the corresponding amides

This research has been financed by MINECO of Spain and AGAUR (Generalitat de Catalunya) through projects CTQ2010-21532-C02-01 and 2014-SGR-149

Royal Society of Chemistry

Director: Ministerio de Ciencia e Innovación (Espanya)
Autor: Ferrer Vall-llosada, Íngrid
Fontrodona, Xavier
Rodríguez Pizarro, Montserrat
Romero García, Isabel
Data: 21 febrer 2016
Resum: The reaction of cis,fac-[RuCl2(dmso-S)3(dmso-O)], 1, with different azole (L) ligands leads to new [RuCl2(L)(dmso-S)3] compounds (L = CH3-pz-H, 2; NO2-pz-H, 3; CF3-pz-H, 4 and Br-Hind, 5). Complexes 2-5 have been characterized by analytical, spectroscopic and electrochemical techniques as well as by monocrystal X-ray diffraction analysis. Upon oxidation to Ru(iii) the complexes undergo linkage isomerization of a S-bound dmso ligand and the corresponding kinetic rates as well as the thermodynamic properties have been determined for compound 2 and also for the previously described [RuIICl2(pypz-H)(dmso-S)2] (pypz-H = 2-(3-pyrazolyl)pyridine), 6, from cyclic voltammetries performed at different scan rates. The exposure of compound 2 to visible light in acetonitrile produces the substitution of one dmso ligand by a solvent molecule generating a new compound, 2′. The irradiation of solutions of compounds 2 and 6 in chloroform leads in both cases to the substitution of one dmso by a chlorido ligand in parallel to the oxidation of Ru(ii) to Ru(iii) generating complexes 2′′ and 6′ respectively. The reactivity of compounds 2-6 has been tested with regard to the hydration of nitriles in water as a solvent, displaying in all cases good performance and selectivity for the corresponding amides
This research has been financed by MINECO of Spain and AGAUR (Generalitat de Catalunya) through projects CTQ2010-21532-C02-01 and 2014-SGR-149
Format: application/pdf
Accés al document: http://hdl.handle.net/10256/13701
Llenguatge: eng
Editor: Royal Society of Chemistry
Col·lecció: info:eu-repo/semantics/altIdentifier/doi/10.1039/c5dt04376j
info:eu-repo/semantics/altIdentifier/issn/1477-9226
info:eu-repo/semantics/altIdentifier/eissn/1477-9234
info:eu-repo/grantAgreement/MICINN//CTQ2010-21532-C02-01/ES/MIMETIZACION DE PROCESOS BIOINORGANICOS Y APLICACIONES CATALITICAS CON COMPUESTOS DE METALES DE TRANSICION./
Drets: Tots els drets reservats
Matèria: Ruteni -- Compostos
Ruthenium compounds
Ruteni -- Compostos -- Síntesi
Ruthenium compounds -- Synthesis
Isomeria
Isomerism
Catàlisi
Catalysis
Títol: Ru(ii)-dmso complexes containing azole-based ligands: Synthesis, linkage isomerism and catalytic behaviour
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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