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Marta E. G. Mosquera, PhD, FRSC, graduated in Chemistry from Oviedo University, where she carried out her doctorate on Ru(II) complexes. After her PhD, she moved to Cambridge University to join Prof. D. S. Wright group where she worked on main group chemistry. After a brief stay in the University of Oviedo as an Assistant Professor, where she worked on diphosphine carbenes, in 2003 she moved to Alcalá University as Associate Professor. In 2020 she was promoted to Full Professor within the Madrid Program for Excellence. Her current fields of research are Organometallic, Coordination and Structural Chemistry, her efforts being oriented towards three different areas: 1. Homo and heterometallic main group compounds active in catalytic polymerization processes and in the generation of new C-C bonds. Aiming in particular to develop catalysts for the generation of bioplastics and valorization of CO2. 2. Design and synthesis of new metal-organic frameworks (MOFs) with transition or main group metals with multifunctionalized ligands. 3. Study of systems with non-covalent interactions such as Halogen Bonding, and the analysis of their influence in the structure and reactivity. Her work has been reported in more than 112 papers and 90 conferences contributions. She has given invited talks both in Spanish Universities and abroad. She has been in the Scientific and/or Organizing Committee of several National and International conferences.
Polymers are essential materials in our daily life. The synthesis of value-added polymers is mainly performed from fossil fuel-derived monomers. However, the adoption of the circular economy model based on the bioeconomy will reduce the dependence on fossil fuels. In this context, biorefineries have emerged to convert biomass into bioenergy and produce high value-added products, including molecules that can be further used as building blocks for the synthesis of biopolymers and bioplastics. The achievement of catalytic systems able to polymerize the natural monomer counterparts, such as terpenes or terpenoids, is still a challenge in the development of polymers with good mechanical, thermal, and chemical properties. This review describes the most common types of bioplastics and biopolymers and focuses specifically on the polymerization of terpenes and terpenoids, which represent a source of promising monomers to create bio-based polymers and copolymers.
Marta. E. G. Mosquera; Gerardo Jiménez; Vanessa Tabernero; Joan Vinueza-Vaca; Carlos García-Estrada; Katarina Kosalková; Alberto Sola-Landa; Belén Monje; Carolina Acosta; Rafael Alonso; Miguel Ángel Valera. Terpenes and Terpenoids: Building Blocks to Produce Biopolymers. Sustainable Chemistry 2021, 2, 467 -492.
AMA StyleMarta. E. G. Mosquera, Gerardo Jiménez, Vanessa Tabernero, Joan Vinueza-Vaca, Carlos García-Estrada, Katarina Kosalková, Alberto Sola-Landa, Belén Monje, Carolina Acosta, Rafael Alonso, Miguel Ángel Valera. Terpenes and Terpenoids: Building Blocks to Produce Biopolymers. Sustainable Chemistry. 2021; 2 (3):467-492.
Chicago/Turabian StyleMarta. E. G. Mosquera; Gerardo Jiménez; Vanessa Tabernero; Joan Vinueza-Vaca; Carlos García-Estrada; Katarina Kosalková; Alberto Sola-Landa; Belén Monje; Carolina Acosta; Rafael Alonso; Miguel Ángel Valera. 2021. "Terpenes and Terpenoids: Building Blocks to Produce Biopolymers." Sustainable Chemistry 2, no. 3: 467-492.
Unusual reversible dehydration-hydration process of a stable bismuth-based hybrid perovskite with good optoelectronic properties and exceptional stability.
Artem A. Babaryk; Yolanda Pérez; Mario Martínez; Marta Elena Gonzalez Mosquera; Marius Zehender; Simon A Svatek; Elisa Antolín; Patricia Horcajada. Reversible dehydration–hydration process in stable bismuth-based hybrid perovskites. Journal of Materials Chemistry C 2021, 1 .
AMA StyleArtem A. Babaryk, Yolanda Pérez, Mario Martínez, Marta Elena Gonzalez Mosquera, Marius Zehender, Simon A Svatek, Elisa Antolín, Patricia Horcajada. Reversible dehydration–hydration process in stable bismuth-based hybrid perovskites. Journal of Materials Chemistry C. 2021; ():1.
Chicago/Turabian StyleArtem A. Babaryk; Yolanda Pérez; Mario Martínez; Marta Elena Gonzalez Mosquera; Marius Zehender; Simon A Svatek; Elisa Antolín; Patricia Horcajada. 2021. "Reversible dehydration–hydration process in stable bismuth-based hybrid perovskites." Journal of Materials Chemistry C , no. : 1.
The antimicrobial lysozyme (Lys) was electrostatically incorporated to negatively charged crosslinked poly(glycidyl methacrylate) (c-PGMA) macromolecular assemblies. The resulting material was characterized by AFM, infrared spectra, water contact angle measurements and the staining with the primary amino specific dye fluorescamine. c-PGMA nanoparticles were successfully loaded with Lys reaching ratios of 27.3 ± 4.0 and 22.5 ± 1.7 mg Lys/g polymer for c-PGMA suspensions and functionalized glass substrates, respectively. Lys-loaded c-PGMA caused clear inhibition zones on S. aureus and E. coli in comparison to neat c-PGMA. c-PGMA functionalized surfaces were intrinsically resistant to colonization, but the incorporation of Lys added resistance to bacterial attachment and allowed keeping surfaces clean of bacterial cells for both strains. A relatively rapid release (24 h) of Lys was observed at physiological pH (7.4). In addition, c-PGMA functionalized substrates could be reloaded several times without losing capacity. c-PGMA macromolecular assemblies did not display cytotoxicity to human dermal fibroblasts as shown in 24 h MTT assays. This work demonstrated that c-PGMA assemblies display durable antibacterial activity, biocompatibility, and full reloading capacity with antimicrobial peptides. c-PGMA functionalized materials have potential application as nanocarriers for anti-infective uses.
Miguel Palenzuela; Laura Valenzuela; Georgiana Amariei; Juan F. Vega; Marta E.G. Mosquera; Roberto Rosal. Poly(glycidyl methacrylate) macromolecular assemblies as biocompatible nanocarrier for the antimicrobial lysozyme. International Journal of Pharmaceutics 2021, 603, 120695 .
AMA StyleMiguel Palenzuela, Laura Valenzuela, Georgiana Amariei, Juan F. Vega, Marta E.G. Mosquera, Roberto Rosal. Poly(glycidyl methacrylate) macromolecular assemblies as biocompatible nanocarrier for the antimicrobial lysozyme. International Journal of Pharmaceutics. 2021; 603 ():120695.
Chicago/Turabian StyleMiguel Palenzuela; Laura Valenzuela; Georgiana Amariei; Juan F. Vega; Marta E.G. Mosquera; Roberto Rosal. 2021. "Poly(glycidyl methacrylate) macromolecular assemblies as biocompatible nanocarrier for the antimicrobial lysozyme." International Journal of Pharmaceutics 603, no. : 120695.
High bacterial inactivation and antifouling activity under UV light irradiation displayed by PANI and PEDOT conducting polymer nanofibers (CPNs).
Srabanti Ghosh; Georgiana Amariei; Marta Elena Gonzalez Mosquera; Roberto Rosal. Conjugated polymer nanostructures displaying highly photoactivated antimicrobial and antibiofilm functionalities. Journal of Materials Chemistry B 2021, 9, 4390 -4399.
AMA StyleSrabanti Ghosh, Georgiana Amariei, Marta Elena Gonzalez Mosquera, Roberto Rosal. Conjugated polymer nanostructures displaying highly photoactivated antimicrobial and antibiofilm functionalities. Journal of Materials Chemistry B. 2021; 9 (21):4390-4399.
Chicago/Turabian StyleSrabanti Ghosh; Georgiana Amariei; Marta Elena Gonzalez Mosquera; Roberto Rosal. 2021. "Conjugated polymer nanostructures displaying highly photoactivated antimicrobial and antibiofilm functionalities." Journal of Materials Chemistry B 9, no. 21: 4390-4399.
Terpenes and their oxygenated derivatives, terpenoids, are synthesized mainly by plants and are found in flowers, fruits, trees and spices. They are one of the largest family of natural products synthesized as secondary metabolites. A remarkable structurally different terpenes can be found, including acyclic, monocyclic, bicyclic and polycyclic structures. In all cases, they present functional groups which render them as interesting precursors for the synthesis of new added-value chemicals. From a chemical point of view, terpenes are hydrocarbon units with double bonds, hence there are suitable natural substitutes of oil-derived monomers; however, terpene polymerization is an area that has been little explored. In this chapter, an overview of the most commonly studied terpenes and terpenoids in polymerization processes catalyzed by metal compounds is given. In some cases, such as the copolymerization of 1,2-limonene-oxide with CO2 to give polycarbonates, polymers that can compete with the oil-derived ones have been produced which shown the great potential that this family of natural products entails. The polymerization of terpenes and terpenoids is an exciting area that is only now awakening.
Miguel Palenzuela; David Sánchez-Roa; Jesús Damián; Valentina Sessini; Marta E.G. Mosquera. Polymerization of terpenes and terpenoids using metal catalysts. Advances in Organometallic Chemistry 2021, 55 -93.
AMA StyleMiguel Palenzuela, David Sánchez-Roa, Jesús Damián, Valentina Sessini, Marta E.G. Mosquera. Polymerization of terpenes and terpenoids using metal catalysts. Advances in Organometallic Chemistry. 2021; ():55-93.
Chicago/Turabian StyleMiguel Palenzuela; David Sánchez-Roa; Jesús Damián; Valentina Sessini; Marta E.G. Mosquera. 2021. "Polymerization of terpenes and terpenoids using metal catalysts." Advances in Organometallic Chemistry , no. : 55-93.
Carbon materials such as carbon graphitic structures, carbon nanotubes, and graphene nanosheets are extensively used as supports for electrocatalysts in fuel cells. Alternatively, conducting polymers displayed ultrahigh electrical conductivity and high chemical stability havegenerated an intense research interest as catalysts support for polymer electrolyte membrane fuel cells (PEMFCs) as well as microbial fuel cells (MFCs). Moreover, metal or metal oxides catalysts can be immobilized on the pure polymer or the functionalized polymer surface to generate conducting polymer-based nanohybrids (CPNHs) with improved catalytic performance and stability. Metal oxides generally have large surface area and/or porous structures and showed unique synergistic effects with CPs. Therefore, a stable, environmentally friendly bio/electro-catalyst can be obtained with CPNHs along with better catalytic activity and enhanced electron-transfer rate. The mass activity of Pd/polypyrrole (PPy) CPNHs as an anode material for ethanol oxidation is 7.5 and 78 times higher than that of commercial Pd/C and bulk Pd/PPy. The Pd rich multimetallic alloys incorporated on PPy nanofibers exhibited an excellent electrocatalytic activity which is approximately 5.5 times higher than monometallic counter parts. Similarly, binary and ternary Pt-rich electrocatalysts demonstrated superior catalytic activity for the methanol oxidation, and the catalytic activity of Pt24Pd26Au50/PPy significantly improved up to 12.5 A per mg Pt, which is approximately15 times higher than commercial Pt/C (0.85 A per mg Pt). The recent progress on CPNH materials as anode/cathode and membranes for fuel cell has been systematically reviewed, with detailed understandings into the characteristics, modifications, and performances of the electrode materials.
Srabanti Ghosh; Suparna Das; Marta E. G. Mosquera. Conducting Polymer-Based Nanohybrids for Fuel Cell Application. Polymers 2020, 12, 2993 .
AMA StyleSrabanti Ghosh, Suparna Das, Marta E. G. Mosquera. Conducting Polymer-Based Nanohybrids for Fuel Cell Application. Polymers. 2020; 12 (12):2993.
Chicago/Turabian StyleSrabanti Ghosh; Suparna Das; Marta E. G. Mosquera. 2020. "Conducting Polymer-Based Nanohybrids for Fuel Cell Application." Polymers 12, no. 12: 2993.
In this work, the polymerization of Limonene Oxide (LO) has been achieved using an Earth abundant metal-based catalyst developed in our group, that is very active in ring opening polymerization (ROP) processes. The bio-based polylimonene ether (PLO) obtained had low molecular weight and good thermal properties, thus being a potential green polymeric additive for other bio-based polymers such as PLA. Hence, we have explored its ability to influence PLA properties. The addition of only 10 wt %, led to the modification and improvement of PLA properties in terms of flexibility, thermal stability, and hydrophobicity. The results obtained are promising and open up the potential industrial application of polylimonene oxide (PLO) for the melt-processing of blends based on PLA/PLO. These new materials are totally based on renewable sources and may be interesting for many applications where biodegradability and reduced water adsorption is required, such as food packaging or agricultural mulch films.
Valentina Sessini; Miguel Palenzuela; Jesús Damián; Marta E.G. Mosquera. Bio-based polyether from limonene oxide catalytic ROP as green polymeric plasticizer for PLA. Polymer 2020, 210, 123003 .
AMA StyleValentina Sessini, Miguel Palenzuela, Jesús Damián, Marta E.G. Mosquera. Bio-based polyether from limonene oxide catalytic ROP as green polymeric plasticizer for PLA. Polymer. 2020; 210 ():123003.
Chicago/Turabian StyleValentina Sessini; Miguel Palenzuela; Jesús Damián; Marta E.G. Mosquera. 2020. "Bio-based polyether from limonene oxide catalytic ROP as green polymeric plasticizer for PLA." Polymer 210, no. : 123003.
Ruthenium coordination compounds have demonstrated a promising anticancer and antibacterial activity, but their poor water solubility and low stability under physiological conditions may limit their therapeutic applications. Physical encapsulation or covalent conjugation with polymers may overcome these drawbacks, but generally involve multistep reactions and purification processes. In this work, the antibacterial activity of the polymeric precursor dicarbonyldichlororuthenium (II) [Ru(CO)2Cl2]n has been studied against Escherichia coli and Staphylococcus aureus. This Ru-carbonyl precursor shows minimum inhibitory concentration at nanogram per millilitre, which renders it a novel antimicrobial polymer without any organic ligands. Besides, [Ru(CO)2Cl2]n antimicrobial activity is markedly boosted under photoirradiation, which can be ascribed to the enhanced generation of reactive oxygen species under UV irradiation. [Ru(CO)2Cl2]n has been able to inhibit bacterial growth via the disruption of bacterial membranes and triggering upregulation of stress responses as shown in microscopic measurements. The activity of polymeric ruthenium as an antibacterial material is significant even at 6.6 ng/mL while remaining biocompatible to the mammalian cells at much higher concentrations. This study proves that this simple precursor, [Ru(CO)2Cl2]n, can be used as an antimicrobial compound with high activity and a low toxicity profile in the context of need for new antimicrobial agents to fight bacterial infections.
Srabanti Ghosh; Georgiana Amariei; Marta E.G. Mosquera; Roberto Rosal. Polymeric ruthenium precursor as a photoactivated antimicrobial agent. Journal of Hazardous Materials 2020, 402, 123788 .
AMA StyleSrabanti Ghosh, Georgiana Amariei, Marta E.G. Mosquera, Roberto Rosal. Polymeric ruthenium precursor as a photoactivated antimicrobial agent. Journal of Hazardous Materials. 2020; 402 ():123788.
Chicago/Turabian StyleSrabanti Ghosh; Georgiana Amariei; Marta E.G. Mosquera; Roberto Rosal. 2020. "Polymeric ruthenium precursor as a photoactivated antimicrobial agent." Journal of Hazardous Materials 402, no. : 123788.
Alkali metal compounds 1–12, with terpene-derived oximate ligands, have been prepared and fully spectroscopically characterized. For derivatives 1–9 aggregation processes are observed in solution. To disfavor these processes and decrease the nuclearity, derivatives 10–12 with crown ethers or cryptands were prepared, which are mononuclear in solution. The activity as ring-opening polymerization (ROP) promoters was assessed for compounds 1–12. In these studies, Na and K compounds proved to be very active and polymerized rac-lactide within minutes. In their activity, the aggregation processes have a clear effect and polymers with molecular weights higher than the theoretical weights are obtained, as a reflection of fewer accessible active centers. This effect is more pronounced at lower temperatures; however, the potassium compound 11, with a crown ether coordinated plus an extra anchoring point in the terpenoid ligand via a pyridine group, is not as heavily affected by the aggregation and is active even at −70 °C. In fact, this potassium compound can promote rac-lactide isoselective polymerization to give highly isotactic polymers, being one of the very few alkali-metal compounds reported that is able to induce such an isoselective process.
María Fernández-Millán; Paula Ortega; Tomás Cuenca; Jesus Cano; Marta E. G. Mosquera. Alkali-Metal Compounds with Bio-Based Ligands as Catalysts for Isoselective Lactide Polymerization: Influence of the Catalyst Aggregation on the Polymerization Control. Organometallics 2020, 39, 2278 -2286.
AMA StyleMaría Fernández-Millán, Paula Ortega, Tomás Cuenca, Jesus Cano, Marta E. G. Mosquera. Alkali-Metal Compounds with Bio-Based Ligands as Catalysts for Isoselective Lactide Polymerization: Influence of the Catalyst Aggregation on the Polymerization Control. Organometallics. 2020; 39 (12):2278-2286.
Chicago/Turabian StyleMaría Fernández-Millán; Paula Ortega; Tomás Cuenca; Jesus Cano; Marta E. G. Mosquera. 2020. "Alkali-Metal Compounds with Bio-Based Ligands as Catalysts for Isoselective Lactide Polymerization: Influence of the Catalyst Aggregation on the Polymerization Control." Organometallics 39, no. 12: 2278-2286.
Cationic 1,2 and 1,3 doubly‐constrained geometry di(silylamido)cyclopentadienyl zirconium complexes, whilst being Group 4 alkyl‐free 14‐electron d 0 species, promote the polymerization of MMA. Different cocatalysts such as B(C 6 F 5 ) 3 , Al(C 6 F 5 ) 3 and [CPh 3 ][B(C 6 F 5 ) 4 ] have been employed to generate the catalytic species in order to collect experimental evidence to propose the polymerization mechanism that these cationic compounds may follow. By systematically studying the role of the active species, this study establishes that the mechanism may be different from the traditional coordination‐addition mechanism proposed for group 4 metal complexes in MMA polymerizations.
Addis M. Londaitsbehere; María Sudupe; Marta E. G. Mosquera; Tomás Cuenca; Jesús Cano. MMA Polymerization with Group 4 Alkyl‐Free 14‐Electron d 0 Species. European Journal of Inorganic Chemistry 2020, 2020, 1589 -1595.
AMA StyleAddis M. Londaitsbehere, María Sudupe, Marta E. G. Mosquera, Tomás Cuenca, Jesús Cano. MMA Polymerization with Group 4 Alkyl‐Free 14‐Electron d 0 Species. European Journal of Inorganic Chemistry. 2020; 2020 (17):1589-1595.
Chicago/Turabian StyleAddis M. Londaitsbehere; María Sudupe; Marta E. G. Mosquera; Tomás Cuenca; Jesús Cano. 2020. "MMA Polymerization with Group 4 Alkyl‐Free 14‐Electron d 0 Species." European Journal of Inorganic Chemistry 2020, no. 17: 1589-1595.
Aluminum complex [AlMeL2] (1), (L = N-(2,6-diisopropylphenyl)-phenoxyimine), promotes the Ring-Opening Polymerization (ROP) of L- and rac-lactide, and the copolymerization of L-lactide with rac-β-butyrolactone and ε-caprolactone. This complex exhibits good control over the ROP of rac-lactide producing heterorich-PLA (Pr = 0.69) with narrow dispersity (ÐM < 1.10). When the ratio of the co-initiator (BnOH) is increased the polymerization is immortal in nature. Furthermore, a series of copolymers PLLA-co-PHB and PLLA-co-PCL with wide ranging monomer compositions were synthesized and characterized by NMR spectroscopy and differential scanning calorimetry (DSC). The microstructure disclosed by 13C NMR analysis suggested a random distribution of the monomers along the polymer chain for both the PLLA-co-PHB and PLLA-co-PCL copolymers. In all cases, the copolymers displayed a single glass transition temperature with values intermediate between those of the corresponding homopolymers and in perfect agreement with the theoretical values calculated by the Fox equation. These data further support the random structure of the PLLA-co-PHB and PLLA-co-PCL copolymers obtained by 1/BnOH. DFT calculations have been carried out to justify the unusual but similar reactivity observed for LA and BBL with the catalyst.
Francisco M. García-Valle; Tomás Cuenca; Marta E.G. Mosquera; Stefano Milione; Jesús Cano. Ring-Opening Polymerization (ROP) of cyclic esters by a versatile aluminum Diphenoxyimine Complex: From polylactide to random copolymers. European Polymer Journal 2020, 125, 109527 .
AMA StyleFrancisco M. García-Valle, Tomás Cuenca, Marta E.G. Mosquera, Stefano Milione, Jesús Cano. Ring-Opening Polymerization (ROP) of cyclic esters by a versatile aluminum Diphenoxyimine Complex: From polylactide to random copolymers. European Polymer Journal. 2020; 125 ():109527.
Chicago/Turabian StyleFrancisco M. García-Valle; Tomás Cuenca; Marta E.G. Mosquera; Stefano Milione; Jesús Cano. 2020. "Ring-Opening Polymerization (ROP) of cyclic esters by a versatile aluminum Diphenoxyimine Complex: From polylactide to random copolymers." European Polymer Journal 125, no. : 109527.
A study on how the covalent character of the halogen bond can be modulated by using different halogen donors.
Silvia Dortéz; Francisco Fernández-Palacio; Jesús Damián; Carlos Gaiteiro; Javier Ramos; Pilar Gómez-Sal; Marta Elena Gonzalez Mosquera. Halogen bonding (HaB) in E–I⋯X–M systems: influence of the halogen donor on the HaB nature. CrystEngComm 2019, 22, 870 -877.
AMA StyleSilvia Dortéz, Francisco Fernández-Palacio, Jesús Damián, Carlos Gaiteiro, Javier Ramos, Pilar Gómez-Sal, Marta Elena Gonzalez Mosquera. Halogen bonding (HaB) in E–I⋯X–M systems: influence of the halogen donor on the HaB nature. CrystEngComm. 2019; 22 (5):870-877.
Chicago/Turabian StyleSilvia Dortéz; Francisco Fernández-Palacio; Jesús Damián; Carlos Gaiteiro; Javier Ramos; Pilar Gómez-Sal; Marta Elena Gonzalez Mosquera. 2019. "Halogen bonding (HaB) in E–I⋯X–M systems: influence of the halogen donor on the HaB nature." CrystEngComm 22, no. 5: 870-877.
This special web collection of Dalton Transactions focuses on the inorganic chemistry of the p-block elements, as a tribute to the 150th anniversary of the development of the periodic table.
Zachariah M. Heiden; Marta E. G. Mosquera; Harkesh B. Singh. Inorganic chemistry of the p-block elements. Dalton Transactions 2019, 48, 6666 -6668.
AMA StyleZachariah M. Heiden, Marta E. G. Mosquera, Harkesh B. Singh. Inorganic chemistry of the p-block elements. Dalton Transactions. 2019; 48 (20):6666-6668.
Chicago/Turabian StyleZachariah M. Heiden; Marta E. G. Mosquera; Harkesh B. Singh. 2019. "Inorganic chemistry of the p-block elements." Dalton Transactions 48, no. 20: 6666-6668.
New aluminates as active catalysts for vinyl polymerization are described, as well as a strategy to crosslinked polymers from GMA in a controlled fashion.
Miguel Palenzuela; Mª Teresa Muñoz; Juan F. Vega; Ángel Gutiérrez Rodríguez; Tomás Cuenca; Marta E. G. Mosquera. Heterobimetallic aluminate derivatives with bulky phenoxide ligands: a catalyst for selective vinyl polymerization. Dalton Transactions 2019, 48, 6435 -6444.
AMA StyleMiguel Palenzuela, Mª Teresa Muñoz, Juan F. Vega, Ángel Gutiérrez Rodríguez, Tomás Cuenca, Marta E. G. Mosquera. Heterobimetallic aluminate derivatives with bulky phenoxide ligands: a catalyst for selective vinyl polymerization. Dalton Transactions. 2019; 48 (19):6435-6444.
Chicago/Turabian StyleMiguel Palenzuela; Mª Teresa Muñoz; Juan F. Vega; Ángel Gutiérrez Rodríguez; Tomás Cuenca; Marta E. G. Mosquera. 2019. "Heterobimetallic aluminate derivatives with bulky phenoxide ligands: a catalyst for selective vinyl polymerization." Dalton Transactions 48, no. 19: 6435-6444.
A series of alkali metal complexes (Li, Na, K) with different fluorinated phenoxo-imine ligands [M{(O-2-(RN═CH)-C6H4}] [R = C6F5; 2,4,6-F3C6H2F3; 2,6-C6H3F2; 2,3-C6H3F2; 2-C6H4F; 2-CF3C6H4CH2; CF3CH2] have been synthesized and fully characterized. By using THF as solvent, suitable crystals for X-ray diffraction analysis were obtained, and the solid state structure of some of the prepared compounds has been determined. This analysis reveals the formation of a C–F bond activation product for the potassium compound with the five-fluorinated ligand. In stronger donor solvents, such as dimethylsulfoxide, this process occurs immediately, independently of the metal used. This C–F activation takes place in a smooth process at room temperature. The nature of this reaction is studied by 1H-DOSY NMR experiments with stoichiometric amounts of DMSO, monitoring the disaggregation process from the initial solution structure to the final activation product. The variation of the number of fluorine atoms and their location in the iminic ring is also studied, showing their influence in this intramolecular C–F bond activation process.
Francisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Marta E. G. Mosquera; Jesús Cano. Intramolecular C–F Activation in Schiff-Base Alkali Metal Complexes. Organometallics 2019, 38, 894 -904.
AMA StyleFrancisco M. García-Valle, Vanessa Tabernero, Tomás Cuenca, Marta E. G. Mosquera, Jesús Cano. Intramolecular C–F Activation in Schiff-Base Alkali Metal Complexes. Organometallics. 2019; 38 (4):894-904.
Chicago/Turabian StyleFrancisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Marta E. G. Mosquera; Jesús Cano. 2019. "Intramolecular C–F Activation in Schiff-Base Alkali Metal Complexes." Organometallics 38, no. 4: 894-904.
New heterometallic aluminium-alkali metal compounds have been prepared using Schiff bases with electron withdrawing substituents as ligands. The synthesis of these new species was achieved via the reaction of AlMe3 with the freshly prepared alkali-metallated ligand. The derivatives formed were characterized by NMR in solution and by single crystal X-ray diffraction in the solid state. Aluminate derivatives with lithium and sodium were prepared and a clear influence of the alkali metal in the final outcome is observed. The presence of a Na···F interaction in the solid state has a stabilization effect and the species [NaAlMe3L]2 can de isolated for the first time, which was not possible when using Schiff bases without electron withdrawing substituents as ligands.
Francisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization. Molecules 2018, 23, 3108 .
AMA StyleFrancisco M. García-Valle, Vanessa Tabernero, Tomás Cuenca, Jesús Cano, Marta E. G. Mosquera. Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization. Molecules. 2018; 23 (12):3108.
Chicago/Turabian StyleFrancisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. 2018. "Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization." Molecules 23, no. 12: 3108.
Investigation of the interaction of a NHC-CDI zwitterion with ZnCl2 in dichloromethane led to the serendipitous discovery of a highly selective, double C–Cl activation of dichloromethane.
David Sanchez-Roa; Tomas G. Santiago; Maria Fernández-Millán; Tomas Cuenca; Pilar Palma; Juan Campora; Marta E. G. Mosquera. Interaction of an imidazolium-2-amidinate (NHC-CDI) zwitterion with zinc dichloride in dichloromethane: role as ligands and C–Cl activation promoters. Chemical Communications 2018, 54, 12586 -12589.
AMA StyleDavid Sanchez-Roa, Tomas G. Santiago, Maria Fernández-Millán, Tomas Cuenca, Pilar Palma, Juan Campora, Marta E. G. Mosquera. Interaction of an imidazolium-2-amidinate (NHC-CDI) zwitterion with zinc dichloride in dichloromethane: role as ligands and C–Cl activation promoters. Chemical Communications. 2018; 54 (89):12586-12589.
Chicago/Turabian StyleDavid Sanchez-Roa; Tomas G. Santiago; Maria Fernández-Millán; Tomas Cuenca; Pilar Palma; Juan Campora; Marta E. G. Mosquera. 2018. "Interaction of an imidazolium-2-amidinate (NHC-CDI) zwitterion with zinc dichloride in dichloromethane: role as ligands and C–Cl activation promoters." Chemical Communications 54, no. 89: 12586-12589.
A new type of -ate derivatives is described, where the alkali metal exerts a strong influence on the final outcome.
Francisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. Schiff-base -ate derivatives with main group metals: generation of a tripodal aluminate metalloligand. Dalton Transactions 2018, 47, 6499 -6506.
AMA StyleFrancisco M. García-Valle, Vanessa Tabernero, Tomás Cuenca, Jesús Cano, Marta E. G. Mosquera. Schiff-base -ate derivatives with main group metals: generation of a tripodal aluminate metalloligand. Dalton Transactions. 2018; 47 (18):6499-6506.
Chicago/Turabian StyleFrancisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. 2018. "Schiff-base -ate derivatives with main group metals: generation of a tripodal aluminate metalloligand." Dalton Transactions 47, no. 18: 6499-6506.
The diphenoxyimine five-coordinated aluminum complex [AlMeL2] (1), (L = N-(2,6-diisopropylphenyl)phenoxyimine), has been synthesized and fully characterized. The mononuclear structure observed in the solid state by X-ray diffraction analysis is maintained in solution, as shown by diffusion-ordered NMR spectroscopy (DOSY). Complex 1 is an active ROP catalyst able to provide well-controlled living ring-opening polymerization of rac-BBL at 100 °C, with PDI = 1.03, in the presence of BnOH to give the biodegrable polyester poly(hydroxybutyrate) (PHB). The suggested active species of this catalytic process, the aluminum complex [Al(OBn)L2] (2), has been synthesized and fully characterized. DFT calculations have been carried out to study the influence of the catalytic active species pocket over the polymer molecular weight control. Moreover, 1 is also active in the copolymerization of rac-β-butyrolactone and l-lactide to provide random copolymers.
Francisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Marta E. G. Mosquera; Jesús Cano; Stefano Milione. Biodegradable PHB from rac-β-Butyrolactone: Highly Controlled ROP Mediated by a Pentacoordinated Aluminum Complex. Organometallics 2018, 37, 837 -840.
AMA StyleFrancisco M. García-Valle, Vanessa Tabernero, Tomás Cuenca, Marta E. G. Mosquera, Jesús Cano, Stefano Milione. Biodegradable PHB from rac-β-Butyrolactone: Highly Controlled ROP Mediated by a Pentacoordinated Aluminum Complex. Organometallics. 2018; 37 (6):837-840.
Chicago/Turabian StyleFrancisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Marta E. G. Mosquera; Jesús Cano; Stefano Milione. 2018. "Biodegradable PHB from rac-β-Butyrolactone: Highly Controlled ROP Mediated by a Pentacoordinated Aluminum Complex." Organometallics 37, no. 6: 837-840.
The new aluminium compounds [AlXMe(OAr)]n (X = Me(1), Cl(2)) bearing the bulky ligand OAr = 2,6-bis(diphenylmethyl)-4-tert-butylphenoxide have been synthesized and characterized in solid state and in solution. These compounds are mononuclear when dissolved. Their catalytic activity in the Glycidyl Methacrylate (GMA) polymerization was explored. This monomer contains two different functionalities: oxirane and methacrylate, hence could give functionalized polymers via ROP or vinyl polymerization. Catalysts 1 and 2 can selectively polymerize the oxirane functionality in minutes at room temperature leaving the methacrylate group intact. Remarkably 1 and 2 are the most active catalysts in ROP processes of GMA described so far.
M. Teresa Muñoz; Miguel Palenzuela; Tomás Cuenca; Marta E. G. Mosquera. Aluminum Aryloxide Compounds as Very Active Catalysts for Glycidyl Methacrylate Selective Ring-Opening Polymerization. ChemCatChem 2018, 10, 936 -939.
AMA StyleM. Teresa Muñoz, Miguel Palenzuela, Tomás Cuenca, Marta E. G. Mosquera. Aluminum Aryloxide Compounds as Very Active Catalysts for Glycidyl Methacrylate Selective Ring-Opening Polymerization. ChemCatChem. 2018; 10 (5):936-939.
Chicago/Turabian StyleM. Teresa Muñoz; Miguel Palenzuela; Tomás Cuenca; Marta E. G. Mosquera. 2018. "Aluminum Aryloxide Compounds as Very Active Catalysts for Glycidyl Methacrylate Selective Ring-Opening Polymerization." ChemCatChem 10, no. 5: 936-939.