Functionalization of Cu3BTC2@IL composites with Pd(II) for catalytic applications

Comunicación en forma de panel presentada en el congreso 2nd European Conference on Metal Organic Frameworks and Porous Polymers del 29 de octubre al 1 denoviembre de 2017 en Delft, HolandaMetal-organic frameworks could be excellent supports for active catalytic species in order to obtain heterogeneous and reusable catalysts, easily removable from the reaction media.[1,2] Additionally, the presence of unsaturated metal centres in their pores provides a superb opportunity to tackle with reactions that requires more than one type of metal centre.[3] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] and [BMIM][PF6] ionic liquids(BMIM= 1-Butyl-3-methylimidazolium). The stability of the composite materials, both chemical and thermal, was studied. Then, the insertion of palladium was made in basic media. By means of EDX the presence of Pd into the structural pores was proved and the quantification was made by ICP-AES. The powder DRX of the Cu3BTC2@[BMIM][Cation]-Pd samples show no structural changes with respect to the pristine Cu3BTC2. The functionalized material was tested as heterogeneous catalyst for Suzuki-Miyaura coupling reactions. The reactions were made in methanol at 70 ºC and using K2CO3 as base. The Pd:substrate molar ratio was set at 0.1 %. The activity was firstly studied using 4-bromotoluene and phenylboronic acid as reagents. The total conversion of the reaction reached 91 % in 1.5 hours with a selectivity towards the cross-coupling product of 67 %. Afterwards, other substrates were tested to study the scope of the reaction. When using 4-bromoanisole and phenylboronic acid, 67% of conversion was reached after 4 hours with a 100 % of selectivity towards the cross-coupling product. References: [1] P. Valvekens, F. Vermoortele and D. D. Vos, Catal. Sci. Technol., 2013, 3, 1435–1445. [2] E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias and M. I. Arriortua, Eur. J. Inorg. Chem., 2015, 2015, 4699–4707. [3] D. Saha, R. Sen, T. Maity and S. Koner, Langmuir, 2013, 29, 3140–3151

Functionalization of Cu3BTC2@IL composites with Pd(II) for catalytic applications

Comunicación en forma de panel presentada en el congreso 2nd European Conference on Metal Organic Frameworks and Porous Polymers del 29 de octubre al 1 denoviembre de 2017 en Delft, HolandaMetal-organic frameworks could be excellent supports for active catalytic species in order to obtain heterogeneous and reusable catalysts, easily removable from the reaction media.[1,2] Additionally, the presence of unsaturated metal centres in their pores provides a superb opportunity to tackle with reactions that requires more than one type of metal centre.[3] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] and [BMIM][PF6] ionic liquids(BMIM= 1-Butyl-3-methylimidazolium). The stability of the composite materials, both chemical and thermal, was studied. Then, the insertion of palladium was made in basic media. By means of EDX the presence of Pd into the structural pores was proved and the quantification was made by ICP-AES. The powder DRX of the Cu3BTC2@[BMIM][Cation]-Pd samples show no structural changes with respect to the pristine Cu3BTC2. The functionalized material was tested as heterogeneous catalyst for Suzuki-Miyaura coupling reactions. The reactions were made in methanol at 70 ºC and using K2CO3 as base. The Pd:substrate molar ratio was set at 0.1 %. The activity was firstly studied using 4-bromotoluene and phenylboronic acid as reagents. The total conversion of the reaction reached 91 % in 1.5 hours with a selectivity towards the cross-coupling product of 67 %. Afterwards, other substrates were tested to study the scope of the reaction. When using 4-bromoanisole and phenylboronic acid, 67% of conversion was reached after 4 hours with a 100 % of selectivity towards the cross-coupling product. References: [1] P. Valvekens, F. Vermoortele and D. D. Vos, Catal. Sci. Technol., 2013, 3, 1435–1445. [2] E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias and M. I. Arriortua, Eur. J. Inorg. Chem., 2015, 2015, 4699–4707. [3] D. Saha, R. Sen, T. Maity and S. Koner, Langmuir, 2013, 29, 3140–3151

Boryl-assisted hydrogenolysis of a nickel–methyl bond

A stable Nickel(II) methyl complex containing a diphosphinoboryl (PBP) pincer ligand is described. Mechanistic studies on the hydrogenolysis of the Ni-Me bond suggest a metal ligand cooperation mechanism that involves the intermediacy of a - B‒H Ni(0) species that further undergoes B‒H oxidative addition to form a Ni(II) hydride complex

Catalytic performance of a new 1D Cu(II) coordination polymer {Cu(NO3)(H2O)}(HTae)(4,4'-Bpy)

Abstract y comunicación en formato poster: 5th International Conference on Multifunctional, Hybrid and Nanomaterials (6-10 March 2017 | Lisbon, Portugal)There has been extensive interest in the synthesis and design of new porous coordination polymers [1] because of their potential applicability in different areas. One interesting crystal engineering approach to construct new coordination polymers is the selection of metal chelating ligands different from those commonly used. [2] In this regard, the β-diketonates, and concretely the metal β-diketonates, have been recently started to be used as structural building blocks in coordination polymers. [3] Deprotonated β-diketonates act as metal chelating agents; hence, in order to obtain extended structures other substituents are necessary to make them act as bridging ligands. This is the case of bis(β-diketonate) 1,1,2,2-tetraacetylethane (H2Tae) which can act as bischelating ligand bridging two metal centres. During the course of our research with the system Cu−Tae−4,4´-Bpy, we have obtained the 1D {Cu(NO3)(H2O)}(HTae)(4,4’-Bpy) coordination polymer.[4] The crystal structure consists in parallel and oblique {Cu(HTae)(4,4’-Bpy)} zig-zag metal-organic chains stacked along the [100] crystallographic direction. Copper atoms are in octahedral coordination environment linked to two nitrogen atoms of two bridging 4,4’-Bipy and to two oxygen atoms of one HTae molecule. The occupation of the other two positions varies from one copper atom to another with different combinations of water and nitrate molecules, giving rise to a commensurate super-structure. By means of thermal removal of water molecules we were able to obtain copper coordinatively unsaturated centres which could act as Lewis acid active sites in several heterogeneous catalytic reactions. Therefore, we have tested the anhydrous compound as heterogeneous catalyst for Knoevenagel condensation reactions. {Cu(NO3)(H2O)}(HTae)(4,4’-Bpy) is an efficient catalyst for the condensation of benzaldehyde and malonitrile in mild conditions (60 ºC in toluene, 5 % catalyst). The scope of the reaction was studied with various substrates. Recycling and leaching tests were also performed.Ministerio de Economía y Competitividad: MAT2013-42092-R Gobierno Vasco: IT-630-13 Dpto. Desarrollo Economico y Competitividad, programa ELKARTEK: ACTIMAT-KK-2015/0009

A Comparison of Hybrid Decision Making Methods for Emergency Support

Abstract A situation consisting in evaluating and choosing among alternative actions can be managed from the point of view of Decision Making (DM). This paper presents an approach to design and develop Decision Support Systems (DSS) to be applied in emergency situations. In these situations the decision maker is under heavy stress because each different decision implies different important outcomes related with human and economic losses. First of all, a domain knowledge base has to be built from both the properties of emergency situations and the actions devoted to counteract them. From this knowledge, three different DM methods, based on the Probability Theory and the Possibility Theory, process the incoming emergency information and choose the best action for putting out the emergency situation. The resulting decisions of each method over a set of plausible emergency situations can be evaluated by a domain expert and the method with the best average performance can be built in the DSS. This DSS can help a decision maker find out an optimal decision in a short period of time maximizing security and minimizing stress.Peer reviewe

Meningitis and subdural empyema as complication of pterygomandibular space abscess upon tooth extraction

Complication of dental infections might be various and heterogeneous. The most common complications are represented by maxilar celulitis, canine space celulitis, infratemporal space celulitis, temporal celulitis and bacteremia. Among rarest complications we found: sepsis, bacterial endocarditis, mediastinitis, intracranial complications, osteomyelitis, etc. Although dental infections are often considered trivial entities, sometimes they can reach an impressive gravity. In this regard, the present study describes a case of dental infection complicated by meningitis, subdural empiema and cerebral vasculitis. Furthermore, we observed other neurological complications, like thalamic ischemic infarction, during the disease evolution. Noteworthy, these entities were not presented when the patient was admitted to hospital. Therefore, the main aim of this report is to highlight the serious consequences that an infection of dental origin could cause

Synthesis, properties, and some rhodium, iridium, and platinum complexes of a series of bulky m-terphenylphosphine ligands

A series of sterically demanding aryl phosphine ligands (L) bearing terphenyl substituents, PR2Ar′ (R = hydrocarbyl, Ar′ = 2,6-diarylphenyl radical) has been prepared and characterized. The stability of these ligands towards oxidation in the air has been tested, and theoretical and experimental studies aimed to provide information on their electronic and steric properties have been performed. Treatment of the metal dimers [MCl(COD)]2(M = Rh, Ir; COD = 1,5-cyclooctadiene) with ligands PMe2ArXyl2(L1) and PMe2ArDipp2(L5), in a 1:1 metal:ligand ratio, afforded the expected square-planar 16-electron complexes [MCl(COD)(PMe2ArXyl2)] and [MCl(COD)(PMe2ArDipp2)], respectively. These compounds were readily converted into the corresponding dicarbonyl derivatives, [MCl(CO)2(PMe2ArXyl2)] and [MCl(CO)2(PMe2ArDipp2)], respectively. While the expected κ1-P coordination mode of the PR2Ar′ ligands is found for these rhodium and iridium species, the mononuclear Pt(II) derivative obtained by reaction of PtCl2with PMe2ArDipp2has composition [PtCl2(PMe2ArDipp2)], and exhibits a bidentate κ1-P, η1-arene coordination mode involving one of the ipso carbon atoms of a flanking terphenyl aryl ring. The corresponding carbonyl compound [PtCl2(CO)(PMe2ArDipp2)], was generated under a CO atmosphere and exhibits κ1-P coordination mode.Ministerio de Ciencia CTQ2013-42501-P, CTQ2014-51912-REDC, CTQ-2014-52769-C3-3-RJunta de Andalucía FQM-119 P09-FQM-4832, FQM-2126European Union 26722

MOF@IL composite materials as Pd(II) supports for heterogeneous organocatalytic reactions

Comunicación Oral realizada en World Congress & Expo on Chemical Engineering & Catalysis (23-24 julio 2018, Osaka, Japón)Metal-Organic Frameworks (MOFs) have experienced a rapid emerge in the last two decades because they offer unique advantages for many applications due to their ordered structures, high thermal stability, tunable chemical functionality, ultra-high porosity and the availability of hundreds of well characterized structures.[1] Among the properties that they may present, they have shown interesting activity as heterogeneous catalysts.[2] Additionally, MOFs could be excellent supports for active catalytic species, due to their porous nature, in order to obtain heterogeneous and reusable catalysts,[3] providing superb opportunities to tackle with reactions that requires more than one type of active centre.[4] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] ionic liquid (BMIM= 1-Butyl-3-methylimidazolium). Then, the insertion of palladium was made in basic media by the formation of a Pd organometallic complex with the N-heterocyclic carbine from the IL. The material was tested as heterogeneous catalyst for several organocatalytic reactions such as Suzuki-Miyaura and Sonogashira cross-coupling reactions, amine alkylation… The different conversion and selectivity results obtained for each type of reaction have allowed analyzing what is the role of each of the metals (Cu and Pd) in each reaction. References [1] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science, 2013, 341(6149), 1230444-01–12; J. Adams, D. Pendlebury, Materials Science & Technology, Thomson Reuters, 2011. [2] P. García-García, M. Müller, A. Corma, Chem. Sci. 2014, 5, 2979–3007; J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su, Chem. Soc. Rev. 2014, 43, 6011–6061. [3] P. Valvekens, F. Vermoortele, D. D. Vos, Catal. Sci. Technol. 2013, 3, 1435–1445; E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias, M. I. Arriortua, Eur. J. Inorg. Chem. 2015, 2015, 4699–4707. [4] D. Saha, R. Sen, T. Maity, S. Koner, Langmuir, 2013, 29, 3140–3151.Aknowledgements: This work has been financially supported by the “Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R (AEI/FEDER, UE)), the “Gobierno Vasco” (Basque University Research System Group, IT-630-13 and Dept. of Economic Development and Competitiveness, ELKARTEK program, LISOL (KK-2016/00095) projects), which we gratefully acknowledge. The authors thank the technicians of SGIker (UPV/EHU)

CPWalker - Plataforma robótica para la rehabilitación y el entrenamiento de la marcha en pacientes con Parálisis Cerebral

Este artículo presenta una plataforma robótica para la rehabilitación post-quirúrgica de personas con parálisis cerebral (PC). La PC define un conjunto de trastornos de la postura y el movimiento que aparece debido a una lesión en el cerebro inmaduro. La cirugía ortopédica es el mejor tratamiento cuando existen problemas musculoesquéleticos severos. La plataforma CPWalker combina un andador inteligente y un exoesqueleto con interfaces avanzados (BCI, EMG) para la interacción humanorobot. En este trabajo se describe tanto el diseño conceptual como el desarrollo de la plataforma CPWalker.Ministerio de Economía y Competitividad (MINECO). Plan Nacional. CP-WalkerPeer Reviewe

A Cationic Unsaturated Platinum(II) Complex that Promotes the Tautomerization of Acetylene to Vinylidene

Complex [PtMe(PMeAr)] (1), which contains a tethered terphenyl phosphine (Ar =2,6-(2,6-PrCH)CH), reacts with [H(EtO)]BAr (BAr =B[3,5-(CF)CH] ) to give the solvent (S) complex [PtMe(S)(PMeAr)] (2⋅S). Although the solvent molecule is easily displaced by a Lewis base (e.g., CO or CH) to afford the corresponding adducts, treatment of 2⋅S with CH yielded instead the allyl complex [Pt(η-CH)(PMeAr)] (6) via the alkyne intermediate [PtMe(η-CH)(PMeAr )] (5). Deuteration experiments with CD, and kinetic and theoretical investigations demonstrated that the conversion of 5 into 6 involves a Pt-promoted HC≡CH to :C=CH tautomerization in preference over acetylene migratory insertion into the Pt−Me bond.Fondos FEDER, Subprogramas Ramón y Cajal and Juan de la Cierva BES - 2011 - 048035Ministerio de Ciencia e Innovación CTQ2013 - 42501- P, CTQ2014 -51912 - REDC, CTQ - 2014 - 52769 - C3 - 3 - RJunta de Andalucía FQM - 119 and project P09 - FQM - 4832 and FQM - 212