dc.contributor.author |
Cánaves, M.M.
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dc.contributor.author |
Cabra, M.I.
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dc.contributor.author |
Bauzá, A.
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dc.contributor.author |
Cañellas, P.
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dc.contributor.author |
Sánchez, K.
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dc.contributor.author |
Orvay, F.
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dc.contributor.author |
García-Raso, A.
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dc.contributor.author |
Fiol, J.J.
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dc.contributor.author |
Terrón, A.
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dc.contributor.author |
Barceló-Oliver, M.
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dc.contributor.author |
Ballester, P.
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dc.contributor.author |
Mata, I.
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dc.contributor.author |
Molins, E.
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dc.contributor.author |
Hussain, F.
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dc.contributor.author |
Frontera, A.
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dc.date.accessioned |
2020-05-05T08:48:48Z |
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dc.identifier.uri |
http://hdl.handle.net/11201/152231 |
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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.format |
application/pdf |
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dc.relation.isformatof |
Versió postprint del document publicat a: https://doi.org/10.1016/j.ccr.2012.12.013 |
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dc.relation.ispartof |
Dalton Transactions, 2014, vol. 43, num. 17, p. 6353-6364 |
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dc.rights |
(c) Cánaves, M.M. et al., 2014 |
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dc.subject.classification |
54 - Química |
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dc.subject.other |
54 - Chemistry. Crystallography. Mineralogy |
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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 |
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dc.type |
info:eu-repo/semantics/article |
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dc.type |
info:eu-repo/semantics/acceptedVersion |
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dc.date.updated |
2020-05-05T08:48:48Z |
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dc.date.embargoEndDate |
info:eu-repo/date/embargoEnd/2026-12-31 |
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dc.embargo |
2026-12-31 |
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dc.subject.keywords |
Pi interactions |
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dc.subject.keywords |
Ab initio calculations |
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dc.subject.keywords |
Noncovalent Interactions |
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dc.subject.keywords |
X-ray structure |
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dc.subject.keywords |
purine and pyrimidine |
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dc.rights.accessRights |
info:eu-repo/semantics/embargoedAccess |
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dc.identifier.doi |
https://doi.org/10.1016/j.ccr.2012.12.013 |
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