Crystal Structures and DFT calculations of new chlorido-dimethylsulfoxide-M(III) (M= Ir, Ru, Rh) complexes with the N-pyrazolyl pyrimidine donor ligand: kinetic vs. thermodynamic isomers

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dc.contributor.author Cánaves, M.M.
dc.contributor.author Cabra, M.I.
dc.contributor.author Bauzá, A.
dc.contributor.author Cañellas, P.
dc.contributor.author Sánchez, K.
dc.contributor.author Orvay, F.
dc.contributor.author García-Raso, A.
dc.contributor.author Fiol, J.J.
dc.contributor.author Terrón, A.
dc.contributor.author Barceló-Oliver, M.
dc.contributor.author Ballester, P.
dc.contributor.author Mata, I.
dc.contributor.author Molins, E.
dc.contributor.author Hussain, F.
dc.contributor.author Frontera, A.
dc.date.accessioned 2020-05-05T08:48:48Z
dc.identifier.uri http://hdl.handle.net/11201/152231
dc.description.abstract [eng] New chlorido-dimethylsulfoxide-iridium(III), ruthenium(III) and rhodium(III) complexes with the 2-(1H-pyrazol-1-yl)-pyrimidine (pyrapyr) ligand (OC-6-N1)-[RhIIICl3(DMSO-κS)(pyrapyr)] (1a, N = 3 and 1b, N = 4); (OC-6-N1)-[RuIIICl3(DMSO-κS)(pyrapyr)] (2a, N = 3 and 2b, N = 4) and (OC-6-N1)-[IrIIICl3(DMSO-κS)(pyrapyr)] (3a, N = 3 and 3b, N = 4) have been synthesized and characterized by spectroscopic techniques and by single crystal X-ray diffraction studies (1a, 1b, 2a, 2b, a disordered crystal 3a/3b and a cocrystal 3a·3b). In all cases, the metal centers show octahedral geometry coordinated to three chloride ligands and one S coordinated dimethylsulfoxide (DMSO-κS). The coordination sphere of the metal is completed by the pyrapyr molecule. Two different coordination modes are observed: (i) the DMSO-κS is opposite to the pyrimidinic N atom (IUPAC nomenclature is OC-6-31 denoted herein as trans); (ii) DMSO-κS is opposite to the pyrazolic N atom (IUPAC nomenclature is OC-6-41 denoted as cis). For Rh(III) the kinetic product (cis) yields the thermodynamic (trans) upon heating a solution of the kinetic product and both isomers have been X-ray characterized. Conversely for Ru(III), both kinetic and thermodynamic complexes have been obtained by using different procedures. Both isomers have been characterized by X-ray crystallography and the kinetic product does not yield the thermodynamic upon heating a solution of the former. Furthermore, the Ir(III) behaves differently, since both isomers are energetically equivalent and both isomers co-crystallize in the solid state. The kinetic/thermodynamic mechanism that yields the different isomers has been studied by using theoretical DFT calculations for each metal. Finally, two Ru(II) complexes (OC-6-N1)-[RuIICl2(DMSO-κS)2(pyrapyr)] (4a, N = 3 and 4b, N = 4) are also described and X-ray characterized. They were obtained as minor products during the synthesis of 2a.
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dc.relation.isformatof Versió postprint del document publicat a: https://doi.org/10.1016/j.ccr.2012.12.013
dc.relation.ispartof Dalton Transactions, 2014, vol. 43, num. 17, p. 6353-6364
dc.rights (c) Cánaves, M.M. et al., 2014
dc.subject.classification 54 - Química
dc.subject.other 54 - Chemistry. Crystallography. Mineralogy
dc.title Crystal Structures and DFT calculations of new chlorido-dimethylsulfoxide-M(III) (M= Ir, Ru, Rh) complexes with the N-pyrazolyl pyrimidine donor ligand: kinetic vs. thermodynamic isomers
dc.type info:eu-repo/semantics/article
dc.type info:eu-repo/semantics/acceptedVersion
dc.date.updated 2020-05-05T08:48:48Z
dc.date.embargoEndDate info:eu-repo/date/embargoEnd/2026-12-31
dc.embargo 2026-12-31
dc.subject.keywords Pi interactions
dc.subject.keywords Ab initio calculations
dc.subject.keywords Noncovalent Interactions
dc.subject.keywords X-ray structure
dc.subject.keywords purine and pyrimidine
dc.rights.accessRights info:eu-repo/semantics/embargoedAccess
dc.identifier.doi https://doi.org/10.1016/j.ccr.2012.12.013


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