Person: Priego Bermejo, José Luis
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First Name
José Luis
Last Name
Priego Bermejo
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Química Inorgánica
Area
Química Inorgánica
Identifiers
16 results
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Item Heteronuclear Dirhodium-Gold Anionic Complexes: Polymeric Chains and Discrete Units(Polymers, 2020) Fernández Bartolomé, Estefanía; Cruz. Paula; Abad Galán, Laura; Cortijo Montes, Miguel; Delgado-Martínez, Patricia; 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 Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks(Crystals, 2019) Prior, David; Cortijo Montes, Miguel; González Prieto, Rodrigo; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José LuisIn this article, we describe the preparation of anionic heteronuclear one-dimensional coordination polymers made by dirhodium paddlewheels and tetracyanido-metallatate building blocks. A series of complexes of (PPh4)2n[{Rh2(µ-O2CCH3)4}{M(CN)4}]n (M = Ni (1), Pd (2), Pt (3)) formulae were obtained by reaction of [Rh2(μ-O2CCH3)4] with (PPh4)2[M(CN)4] in a 1:1 or 2:1 ratio. Crystals of 1−3 suitable for single crystal X-ray diffraction were grown by slow diffusion of a dichloromethane solution of the dirhodium complex into a chloroform solution of the corresponding tetracyanido–metallatate salt. Compounds 1 and 2 are isostructural and crystallize in the triclinic P-1 space group, while compound 3 crystallizes in the monoclinic P21/n space group. A detailed description of the structures is presented, including the analysis of the packing of anionic chains and PPh4+ cations.Item 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; Torres, Marisa RosarioMicrowave 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 Tuning of Adsorption and Magnetic Properties in a Series of Self-Templated Isostructural Ni(II) Metal−Organic Frameworks(Crystal Growth and Design, 2013) Cortijo Montes, Miguel; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José Luis; Torroba, JavierAn isomorphous series of five metal–organic frameworks of formula [Ni4(O2CR)(OH)2(4-pyc)5] [4-pyc = 4-pyridinecarboxylate or isonicotinate; R = C6H5 (1), 4-OMe-C6H4 (2), 2,6-(OMe)2-C6H3 (3), 3,5-(OMe)2-C6H3 (4), 3,4,5-(OMe)3-C6H2 (5)] were obtained by solvothermal reactions. These compounds display a three-dimensional framework where the nickel atoms are coordinated to the hydroxyde anions and two different organic ligands: isonicotinate and phenylcarboxylate. Both hydroxyde (μ3-OH) and phenylcarboxylate (μ3-1κO,2κO,3κO′) ligands are coordinated to nickel atoms of the same secondary building unit (SBU). The SBU consists of four edge-sharing NiA6 octahedra (A = O, N). The isonicotinate ligands, however, act as linkers between SBUs displaying three different coordination modes: μ-1κN,2κO; μ3-1κN,2κO,3κO′; and μ4-1κN,2:3κ2O,4κO′. Nitrogen adsorption measurements were done to obtain textural parameters of these microporous networks. Micropore size distributions indicate cylindrical pores with diameters of approximately 0.80 nm. The values of Brunauer–Emmett–Teller surface areas (SBET) obtained are in the range of 382–488 m2/g, and the micropore volumes are between 0.13 cm3/g and 0.19 cm3/g. Both parameters are influenced by the substitution grade and position of the methoxy groups of the phenylcarboxylate ligand. The magnetic properties, which also depend on the arylcarboxylate ligands, vary from compound 1 (with only antiferromagnetic interactions) to compound 5, which shows a spin glass behavior (Tg = 15 K).- Project number: 52
Item I.amAble: El aprendizaje en ciencias al servicio de la inclusión educativa(2019) Herrero Domínguez, Santiago; Corrales Castellanos, María Eugenia; Sobrino Díaz, María Lourdes; Cilleros Prados, Olga; Barba Fernández, Carmen; Azor Lafarga, Alberto Eduardo; Hernández Díaz, María Yolanda; Martínez Del Pozo, Álvaro; Ranchal Sánchez, Rocío; Maestre Varea, David; Méndez Pozo, Gonzalo Rubén; Gervás Gómez-Navarro, Pablo; Pastor Gil, Lorena; Taravillo Corralo, Mercedes; Guerrero Martínez, Andrés; Sánchez Benítez, Francisco Javier; Martín Conde, María; Priego Bermejo, José Luis; González Prieto, Rodrigo; Jiménez Aparicio, Reyes; Álvarez Serrano, Inmaculada; Cortés Gil, Raquel; Osío Barcina, José De Jesús; Mancheño Real, María José; Arribas Fernández, Paula; Lobato Fernández, Álvaro; Sánchez Arroyo, Antonio José; Torrecilla Manresa, Sofía; Cárdenas Bonett, Marlón Félix; Desvoyes, Benedicte; Bárcena Espelleta, Araceli; Nacenta Torres, Pablo; Rubio Lago, Luis; Bautista Blasco, Susana; Julián Cortés, Alvaro; Arancibia Llaneza, Julieta Noelia; Lombraña Pascual, Rodrigo; Catalán Torrecilla, Cristina; Gutiérrez Franco, Yanna María; Martínez Ruiz, María PalomaI.amAble es un proyecto que nació con una filosofía centrada en la utilización de acciones de solidaridad como método de aprendizaje. Se diseñan y organizan talleres científicos inclusivos para realizarlos en parejas formadas por personas con discapacidad cognitiva y de educación secundaria ordinaria. Se pretende aprender a la vez que se da un servicio a la universidad y a la sociedad, y ese es el espíritu que se ha seguido manteniendo durante esta tercera edición del curso 2018-2019. Item One‐Dimensional [Ni(O2CR)2(NN)x] Polymers: Structural, Magnetic, and Density Functional Theory Studies(ChemPlusChem, 2014) Cortijo Montes, Miguel; Herrero Domínguez, Santiago; Jerez, Belén; 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 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; Torralvo, Maria José; Torroba, JavierSeveral 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.Item Synthesis, Crystal Structure, and Magnetic Properties of Amidate and Carboxylate Dimers of Ruthenium(Crystals, 2017) Delgado Martínez, Patricia; Freire, Carlos; González Prieto, Rodrigo; Jiménez Aparicio, Reyes; Priego Bermejo, José Luis; Torres, M. RosarioSolvothermal and microwave-assisted methods have been used to prepare several amidate and carboxylate complexes of the type [Ru2X(µ-NHOCC6H3-3,5-(OMe)2)4]n [X = Cl (1), Br (2), I (3)] and [Ru2X(µ-O2CC6H3-3,5-(OMe)2)4]n [X = Cl (4), Br (5), I (6)]. Complexes 4–6 have also been obtained by conventional synthesis which is ineffective to prepare the amidate compounds. However, single crystals of complexes 1–5 were obtained using the solvothermal method. The single crystal X-ray structure determination of compounds 1–5 have been carried out. All complexes display a paddlewheel-type structure with the metal atoms connected by four bridging amidate or carboxylate ligands. Chloride, bromide, or iodide anions connect the dimetallic units, producing one-dimensional zigzag chains. The magnetic properties of all compounds were studied. The magnetic moment at room temperature are in accordance with an electronic configuration with three unpaired electrons σ2π4δ2(π*δ*)3 per dimer unit. The fit of the magnetic data suggests the existence, in these complexes, of a weak antiferromagnetic intermolecular interaction between the diruthenium units mediated by the halide ligand and an appreciable zero-field splitting in the diruthenium moieties.