Person: Jiménez Aparicio, Reyes
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First Name
Reyes
Last Name
Jiménez Aparicio
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Química Inorgánica
Area
Química Inorgánica
Identifiers
9 results
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Now showing 1 - 9 of 9
Item Trapping Ag(I) ions by a Pd8 metallacrown molecule to form an unusual nonanuclear AgPd8 cation(Inorganica Chimica Acta, 2019) Calleja, Fernando B.; Cortijo Montes, Miguel; Perles Hernáez, Josefina; Herrero Domínguez, Santiago; Jiménez Aparicio, ReyesThe {[Pd(µ-SC6F5)(µ-dppm)Pd](µ-SC6F5)}4 (dppm = methanediylbis(diphenylphosphane)) (Pd8) metallacrown traps Ag(I) cations giving {Ag[Pd(µ3-SC6F5)(µ-dppm)Pd]4(µ-SC6F5)4}(X) (X = SO3CF3− (AgPd8a), SbF6− (AgPd8b) and ClO4− (AgPd8c)) and {Ag[Pd(µ3-SC6F5)(µ-dppm)Pd]4(µ-SC6F5)4}2[Pt(C6F5)4] (AgPd8d). The insertion of silver increases significantly the stability of the cluster that is stable in solution even in the presence of light, because of the macrocyclic effectItem Tetracarbonatodiruthenium Fragments and Lanthanide(III) Ions as Building Blocks to Construct 2D Coordination Polymers(Polymers, 2019) Gutiérrez Martín, Daniel; Cortijo Montes, Miguel; Martín Humanes, Álvaro; González Prieto, Rodrigo; Delgado Martínez, Patricia; Herrero Domínguez, Santiago; Priego Bermejo, José Luis; Jiménez Aparicio, ReyesTwo-dimensional coordination polymers of [Pr(DMSO)2(OH2)3][Ru2(CO3)4(DMSO)(OH2)]·5H2O (Prα) and [Ln(OH2)5][Ru2(CO3)4(DMSO)]·xH2O (Ln = Sm (Smβ), Gd (Gdβ)) formulae have been obtained by reaction of the corresponding Ln(NO3)3·6H2O dissolved in dimethyl sulphoxide (DMSO) and K3[Ru2(CO3)4]·4H2O dissolved in water. Some DMSO molecules are coordinated to the metal atoms reducing the possibilities of connection between the [Ru2(CO3)4]3− and Ln3+ building blocks giving rise to the formation of two-dimensional networks. The size of the Ln3+ ion and the synthetic method seem to have an important influence in the type of two-dimensional structure obtained. Slow diffusion of the reagents gives rise to Prα that forms a 2D net that is built by Ln3+ ions as triconnected nodes and two types of Ru25+ units as bi- and tetraconnected nodes with (2-c)(3-c)2(4-c) stoichiometry (α structure). An analogous synthetic procedure gives Smβ and Gdβ that display a grid-like structure, (2-c)2(4-c)2, formed by biconnected Ln3+ ions and two types of tetraconnected Ru25+ fragments (β structure). The magnetic properties of these compounds are basically explained as the sum of the individual contributions of diruthenium and lanthanide species, although canted ferrimagnetism or weak ferromagnetism are observed at low temperature.Item Microwave and solvothermal methods for the synthesis of nickel and ruthenium complexes with 9-anthracene carboxylate ligand(Inorganica Chimica Acta, 2015) Cortijo Montes, Miguel; Delgado-Martínez, Patricia; González Prieto, Rodrigo; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José Luis; M.R. TorresMicrowave and solvothermal activation processes have been explored as tools for the preparation of various nickel and ruthenium complexes. Different reaction conditions are tested using ethanol or water as solvents. Three nickel derivatives, [Ni(9-atc)2(OH2)2(py)2]·2EtOH (1), [Ni2(9-atc)4(OH2)(py)4]·2H2O (2·2H2O), and [Ni2(9-atc)4(py)2] (3), and two diruthenium compounds, {[Ru2Cl(9-atc)4]·2H2O}n (4) and [Ru2(9-atc)4(EtOH)2]·2EtOH (5), are obtained. The crystal structure determination of complexes 1-3 and 5 is also described. Compound 1 displays a 1D extended supramolecular structure with hydrogen bonds involving crystallization solvent molecules. Compound 2 is dimetallic, and both nickel centers show an octahedral coordination environment, whereas complexes 3 and 5 display a typical carboxylate-bridged paddlewheel-type structure with two metal atoms connected by four bridging carboxylate ligands. All compounds show weak antiferromagnetic interactions except 3, where a strong intra-dimer antiferromagnetic coupling is observed. Compound 4 also shows a strong zero field splitting.Item Heteronuclear Dirhodium-Gold Anionic Complexes: Polymeric Chains and Discrete Units(Polymers, 2020) Fernández Bartolomé, Estefanía; Paula Cruz; Abad Galán, Laura; Cortijo Montes, Miguel; Patricia Delgado-Martínez; González Prieto, Rodrigo; Priego Bermejo, José Luis; Jiménez Aparicio, ReyesIn this article, we report on the synthesis and characterization of the tetracarboxylatodirhodium(II) complexes [Rh2(μ–O2CCH2OMe)4(THF)2] (1) and [Rh2(μ–O2CC6H4–p–CMe3)4(OH2)2] (2) by metathesis reaction of [Rh2(μ–O2CMe)4] with the corresponding ligand acting also as the reaction solvent. The reaction of the corresponding tetracarboxylato precursor, [Rh2(μ–O2CR)4], with PPh4[Au(CN)2] at room temperature, yielded the one-dimensional polymers (PPh4)n[Rh2(μ–O2CR)4Au(CN)2]n (R = Me (3), CH2OMe (4), CH2OEt (5)) and the non-polymeric compounds (PPh4)2{Rh2(μ–O2CR)4[Au(CN)2]2} (R = CMe3 (6), C6H4–p–CMe3 (7)). The structural characterization of 1, 3·2CH2Cl2, 4·3CH2Cl2, 5, 6, and 7·2OCMe2 is also provided with a detailed description of their crystal structures and intermolecular interactions. The polymeric compounds 3·2CH2Cl2, 4·3CH2Cl2, and 5 show wavy chains with Rh–Au–Rh and Rh–N–C angles in the ranges 177.18°–178.69° and 163.0°–170.4°, respectively. A comparative study with related rhodium-silver complexes previously reported indicates no significant influence of the gold or silver atoms in the solid-state arrangement of these kinds of complexes.Item One‐Dimensional [Ni(O2CR)2(NN)x] Polymers: Structural, Magnetic, and Density Functional Theory Studies(ChemPlusChem, 2014) Cortijo Montes, Miguel; Herrero Domínguez, Santiago; Belén Jerez; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José Luis; Tortajada Pérez, JoséFive nickel complexes, [Ni2(3,4,5-tmb)4(4,4 ′-bpy)] (1), [Ni2(2-ntc)4(4,4 ′-bpy)] (2), [Ni(9-atc)2(4,4 ′-bpy)] (3), [Ni(3,4,5-tmb)2(t-bpee) ] (4), and [Ni2(2-ntc)4(t-bpee)2] (5) (3,4,5-tmb=3,4,5-trimethoxybenzoate; 2-ntc=2-naphthalenecarboxylate; 9-atc=9-anthracenecarboxylate; 4,4 ′-bpy=4,4 ′-bipyridine; t-bpee=trans-1,2-bis(4-pyridyl)ethylene), are prepared. They are characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal and powder X-ray diffraction. 1 and 2 form linear chains of paddlewheel units joined by 4,4 ′-bpy ligands; 3 and 4 display zigzag chains formed by cis-bis(chelate) Ni(O2CR)2 units joined by 4,4 ′-bpy and t-bpee, respectively; and the structure of 5 consists of double chains. The magnetic behavior of the compounds is also studied, and DFT calculations using the broken-symmetry approximation are performed to gain a better understanding of the strong antiferromagnetism found in 1. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Item The use of amidinate ligands in paddlewheel diruthenium chemistry(Coordination Chemistry Reviews, 2019) Cortijo Montes, Miguel; González Prieto, Rodrigo; Herrero Domínguez, Santiago; Priego Bermejo, José Luis; Jiménez Aparicio, ReyesThe amidinate anions have been widely used in the formation of dinuclear complexes with paddlewheel structure. The higher donor character of this type of ligands, compared to carboxylate ligands, increases the electronic density of the dimetallic units giving, in the case of ruthenium, stable complexes with a large variety of oxidation states containing Ru24+, Ru25+ and Ru26+ units. Even complexes with Ru22+, Ru23+ and Ru27+ cores have been detected in electrochemical measurements and isolated in some cases. The influence of formamidinate and benzamidinate ligands in the synthesis, characterization, properties and reactivity of metal-metal bonded diruthenium complexes with paddlewheel structure in several oxidation states is considered. A revision of the electronic and magnetic properties of diruthenium complexes and their relationship with the different electronic configurations found in this type of complexes is broadly documented. Additionally, the switching between oxidation states is considered through the discussion of the results obtained by electrochemical measurements. Finally, the most relevant applications of the amidinatodiruthenium complexes are also reviewed.Item Modulation of the Magnetic Properties of Two-Dimensional Compounds [NiX2(N–N)] by Tailoring Their Crystal Structure(Inorganic Chemistry, 2013) Cortijo Montes, Miguel; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Emilio MatesanzA series of 2-D nickel compounds with the stoichiometry [NiCl 2(N-N)] has been prepared, [N-N = pyrazine (1), 4,4′-bipyridine (2), trans-4,4′-azopyridine (3), trans-1,2-bis(4-pyridyl)ethylene (4), and 1,2-bis(4-pyridyl)ethane (5)]. The complex [NiBr2(4,4′-bpy) ] (6) was also obtained for comparative reasons. Compound 2 is the β phase of the previously reported complex [NiCl2(4,4′-bpy)]. The syntheses of complexes 1-6 were carried out using solvothermal and microwave techniques. The compounds have been characterized by elemental analysis, infrared spectroscopy, thermogravimetry, and powder X-ray diffraction. The crystal structures of compounds 1, 4, and 5 have been solved using ab initio X-ray powder diffraction methods. Compounds 1-6 show the same arrangement, and their structures are described as layers formed by [NiX2] chains linked perpendicularly by N-N ligands. The magnetic properties of the compounds are explained as a balance between the ferromagnetic interactions along the [NiX2] chains and the antiferromagnetic interactions between chains from different layers. This work demonstrates that this balance can be tuned by the length of the N-N ligand. © 2013 American Chemical Society.Item Ultrasound-assisted synthesis of water-soluble monosubstituted diruthenium compounds(Ultrasonics Sonochemistry, 2021) Terán More, Aaron; Cortijo Montes, Miguel; Gutiérrez Alonso, Ángel; Sánchez Peláez, Ana Edilia; Herrero Domínguez, Santiago; Jiménez Aparicio, ReyesThe elusive monosubstituted diruthenium complexes [Ru2Cl(DAniF)(O2CMe)3] (1), [Ru2Cl(DPhF)(O2CMe)3] (2), [Ru2Cl(D-p-CNPhF)(O2CMe)3] (3), [Ru2Cl(D-o-TolF)(O2CMe)3] (4), [Ru2Cl(D-m-TolF)(O2CMe)3] (5), [Ru2Cl(D-p-TolF)(O2CMe)3] (6) and [Ru2Cl(p-TolA)(O2CMe)3] (7) have been synthesized using for the first time ultrasound-assisted synthesis to carry out a substitution reaction in metal–metal bonded dinuclear compounds (DAniF− = N,N′-bis(4-anisyl)formamidinate; DPhF− = N,N′-diphenylformamidinate; D-p-CNPhF− = N,N′-bis(4-cyanophenyl)formamidinate; D-o/m/p-TolF− = N,N′-bis(2/3/4-tolyl)formamidinate; p-TolA− = N-4-tolylamidate). This is a simpler and greener method than the tedious procedures described in the literature, and it has permitted to obtain water-soluble complexes with good yields in a short period of time. A synthetic study has been implemented to find the best experimental conditions to prepare compounds 1–7. Two different types of ligands, formamidinate and amidate, have been used to check the generality of the method for the preparation of monosubstituted complexes. Five new compounds (2–6) have been obtained using a formamidinate ligand, the synthesis of the previously described compound 1 has been improved, and an unprecedented monoamidate complex has been achieved (7). The crystal structures of compounds 3 and 7 have been solved by single crystal X-ray diffraction. These compounds show the typical paddlewheel structure with three acetate ligands and one formamidinate (3) or amidate (7) bridging ligand at the equatorial positions. The axial positions are occupied by the chloride ligand giving rise to one-dimensional polymer structures that were previously unknown for monosubstituted compounds.Item Hybrid Polyfunctional Systems Based on Nickel(II) Isonicotinate(European Journal of Inorganic Chemistry, 2013) Cortijo Montes, Miguel; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José Luis; M. José Torralvo; Javier TorrobaSeveral metal–organic frameworks of nickel(II) were obtained starting from the molecular complex 1, [Ni(OH2)4(4-pyc)2] (4-pyc = 4-pyridinecarboxylate or isonicotinate). By using different reaction conditions, two polymorphs of the anhydrous complex [Ni(4-pyc)2]n (2a and 2b) and the polynuclear compound [Ni5(OH2)3(4-pyc)10]n (3) were obtained in very high yield. All of the compounds were characterized by elemental analysis and spectroscopic data. The crystal structure determination of compounds 2b and 3 was also carried out. Structural and topological analysis of these new structural types and other related ones were performed. It was found that compounds 2a and 2b are a rare case of coordination framework isomers. Thermogravimetric studies indicate that compounds 2b and 3 lose the pore-allocated solvent molecules at moderate temperatures without any significant structural change, and at higher temperatures, compounds 1 and 3 are transformed into 2a. Textural parameters that characterize the microporous networks for 2b and 3 were obtained by nitrogen-adsorption measurements. For both samples, the micropore size distribution indicates cylindrical pores with diameters of 0.85 (2b) and 0.90 nm (3). The values of Brunauer–Emmett–Teller and Langmuir surface areas are 178 and 185 m2 g–1 for compound 2b, and 995 and 982 m2 g–1 for compound 3. Micropore volumes are 0.065 and 0.350 cm3 g–1 for 2b and 3, respectively. The magnetic properties of compounds 1, 2a, and 2b are consistent with the presence of zero-field splitting and a small antiferromagnetic coupling between the metal atoms. The magnetic properties of the pentanuclear compound 3 were analyzed by considering one monomer with zero-field splitting caused by axially distorted NiII octahedral compounds, and two dimeric fragments with magnetic interactions within each dimetallic unit.