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Present position Associate Professor of General and Inorganic Chemistry at Department of Chemistry and Biology "Adolfo Zambelli" University of Salerno Education, Scientific and Professional Experience 06/2013-0872013 Visiting professor at University of Heidelberg in the group of Prof. Dr. Lutz H. Gade(Alexander von Humboldt Return Fellowship). 06/2013-0872013 Visiting professor at Tecnische Univerität München in the group of Prof. Dr. B. Rieger (Alexander von Humboldt Return Fellowship). 06/2005-12/2006 Alexander von Humboldt fellow in the group of Prof. Dr. L. H. Gade at University of Heidelberg (Germany) 01/2005 Assistant Professor at University of Salerno 11/1999 - 03/2003 Ph.D. at the Department of Chemistry, University of Salerno under the supervision of Prof. A. Proto Ph.D. 07/2001 - 06/2002 Research work at the University of Mainz (Germany), in the Department of Inorganic and Analytic Chemistry under the supervision of Prof. Dr. Jun Okuda in the framework of the “International Max Planck Research School for Polymer Materials Science”. 11/1992 - 12/1998 Degree in Chemistry at the University of Salerno. Scientific Interests: Synthesis and characterization of new ligands and transition metal complexes with potential catalytic activity in polymerization and in the reactivity with carbon dioxide. Synthesis and characterization of new nanostructured materials via organometallic catalysis -New elastomeric materials from renewable sources
The synthesis of polymeric materials starting from CO2 as a feedstock is an active task of research. In particular, the copolymerization of CO2 with epoxides via ring-opening copolymerization (ROCOP) offers a simple, efficient route to synthesize aliphatic polycarbonates (APC). In many cases, APC display poor physical and chemical properties, limiting their range of application. The terpolymerization of CO2 with epoxides and organic anhydrides or cyclic esters offers the possibility, combining the ROCOP with ring-opening polymerization (ROP), to access a wide range of materials containing polycarbonate and polyester segments along the polymer chain, showing enhanced properties with respect to the simple APC. This review will cover the last advancements in the field, evidencing the crucial role of the catalytic system in determining the microstructural features of the final polymer.
David Hermann Lamparelli; Carmine Capacchione. Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters. Catalysts 2021, 11, 961 .
AMA StyleDavid Hermann Lamparelli, Carmine Capacchione. Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters. Catalysts. 2021; 11 (8):961.
Chicago/Turabian StyleDavid Hermann Lamparelli; Carmine Capacchione. 2021. "Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters." Catalysts 11, no. 8: 961.
Synthesis and characterization of new dinuclear iron complexes for the coupling of CO2 with epoxides. A bimetallic cooperative reaction mechanism is proposed on the basis of kinetic analyses.
Veronica Paradiso; Francesco Della Monica; David Hermann Lamparelli; Sara D'Aniello; Bernhard Rieger; Carmine Capacchione. Dinuclear [OSSO]-Fe complexes for the reaction of CO2 with epoxides. Catalysis Science & Technology 2021, 1 .
AMA StyleVeronica Paradiso, Francesco Della Monica, David Hermann Lamparelli, Sara D'Aniello, Bernhard Rieger, Carmine Capacchione. Dinuclear [OSSO]-Fe complexes for the reaction of CO2 with epoxides. Catalysis Science & Technology. 2021; ():1.
Chicago/Turabian StyleVeronica Paradiso; Francesco Della Monica; David Hermann Lamparelli; Sara D'Aniello; Bernhard Rieger; Carmine Capacchione. 2021. "Dinuclear [OSSO]-Fe complexes for the reaction of CO2 with epoxides." Catalysis Science & Technology , no. : 1.
A new class of zirconium and hafnium complexes coordinated by linear dianonic tetradentate NSSN ligands is reported. The ligands feature two amide functions coupled with two thioether groups linked by a central flexible ethane bridge and two lateral rigid phenylene bridges and differ for the substituents on the aniline nitrogen atoms, i.e., isopropyl, cyclohexyl, or mesityl substituents: NSSN-iPr, NSSN-Cy, or NSSN-Mes. They were prepared by reacting 2-aminothiophenol with dibromoethane to afford the NSSN ligands without substituents on the aniline nitrogen atoms, which were subsequently alkylated through a reductive amination of acetone or cyclohexanone or palladium-catalyzed cross-coupling reaction with mesityl bromide. The corresponding zirconium and hafnium complexes 1–5 were obtained through a transamination reaction between the neutral ligands and Zr(NMe2)4 or Hf(NMe2)4 [(NSSN-iPr)Zr(NMe2)2 (1), (NSSN-Cy)Zr(NMe2)2 (2), (NSSN-Mes)Zr(NMe2)2 (3), (NSSN-iPr)Hf(NMe2)2 (4), and (NSSN-Cy)Hf(NMe2)2 (5)]. They were characterized in solution by NMR spectroscopy and in solid state by X-ray diffraction analysis (except for 3). All complexes present an octahedral coordination geometry with a fac–fac ligand wrapping and a cis relationship between the other two monodentate ligands. The catalytic performances of 1–5 in the ring-opening polymerization of cyclic esters were investigated. Complex 1 was the most active: its polymerization activity was superior to those generally displayed by zirconium complexes featuring OSSO ligands and compared well with those of the most active group 4 complexes operating in a toluene solution.
Salvatore Impemba; Giuseppina Roviello; Stefano Milione; Carmine Capacchione. NSSN-Type Group 4 Metal Complexes in the Ring-Opening Polymerization of l-Lactide. Inorganic Chemistry 2021, 60, 7561 -7572.
AMA StyleSalvatore Impemba, Giuseppina Roviello, Stefano Milione, Carmine Capacchione. NSSN-Type Group 4 Metal Complexes in the Ring-Opening Polymerization of l-Lactide. Inorganic Chemistry. 2021; 60 (10):7561-7572.
Chicago/Turabian StyleSalvatore Impemba; Giuseppina Roviello; Stefano Milione; Carmine Capacchione. 2021. "NSSN-Type Group 4 Metal Complexes in the Ring-Opening Polymerization of l-Lactide." Inorganic Chemistry 60, no. 10: 7561-7572.
Soluble heterocomplexes consisting of sodium hydride in combination with trialkylaluminum derivatives have been used as anionic initiating systems at 100 °C in toluene for convenient homo-, co- and ter-polymerization of myrcene with styrene and isoprene. In this way it has been possible to obtain elastomeric materials in a wide range of compositions with interesting thermal profiles and different polymeric architectures by simply modulating the alimentation feed and the (monomers)/(initiator systems) ratio. Especially, a complete study of the myrcene-styrene copolymers (PMS) was carried out, highlighting their tapered microstructures with high molecular weights (up to 159.8 KDa) and a single glass transition temperature. For PMS copolymer reactivity ratios, rmyr = 0.12 ± 0.003 and rsty = 3.18 ± 0.65 and rmyr = 0.10 ± 0.004 and rsty = 3.32 ± 0.68 were determined according to the Kelen–Tudos (KT) and extended Kelen–Tudos (exKT) methods, respectively. Finally, this study showed an easy accessible approach for the production of various elastomers by anionic copolymerization of renewable terpenes, such as myrcene, with commodities.
David Lamparelli; Magdalena Kleybolte; Malte Winnacker; Carmine Capacchione. Sustainable Myrcene-Based Elastomers via a Convenient Anionic Polymerization. Polymers 2021, 13, 838 .
AMA StyleDavid Lamparelli, Magdalena Kleybolte, Malte Winnacker, Carmine Capacchione. Sustainable Myrcene-Based Elastomers via a Convenient Anionic Polymerization. Polymers. 2021; 13 (5):838.
Chicago/Turabian StyleDavid Lamparelli; Magdalena Kleybolte; Malte Winnacker; Carmine Capacchione. 2021. "Sustainable Myrcene-Based Elastomers via a Convenient Anionic Polymerization." Polymers 13, no. 5: 838.
Since the report of the stereospecific polymerization of styrene dated 2003, metal complexes bearing [OSSO]-bisphenolate ligands have been successfully applied in different branches of homogeneous catalysis, de facto building a new research field. This review will focus on polymerization reactions promoted by these complexes, starting with those involving “traditional” monomers (such as fossil-derived olefins) up to more recent and green applications, like polymerization of terpenes or utilization of CO2 as a green building block.
Veronica Paradiso; Vito Capaccio; David Hermann Lamparelli; Carmine Capacchione. [OSSO]-bisphenolate metal complexes: A powerful and versatile tool in polymerization catalysis. Coordination Chemistry Reviews 2020, 429, 213644 .
AMA StyleVeronica Paradiso, Vito Capaccio, David Hermann Lamparelli, Carmine Capacchione. [OSSO]-bisphenolate metal complexes: A powerful and versatile tool in polymerization catalysis. Coordination Chemistry Reviews. 2020; 429 ():213644.
Chicago/Turabian StyleVeronica Paradiso; Vito Capaccio; David Hermann Lamparelli; Carmine Capacchione. 2020. "[OSSO]-bisphenolate metal complexes: A powerful and versatile tool in polymerization catalysis." Coordination Chemistry Reviews 429, no. : 213644.
The polymerization of bio-renewable terpenes such as β-ocimene (O), β-myrcene (M), and β-farnesene (F) promoted by CoCl2(PCyPh2)2 (1) in combination with modified methylalumoxane at room temperature is reported. Stereoregular polymers of O, M, and F were obtained. 1 also promoted, showing good stereoselectivity, the copolymerization of O and M with butadiene (B) in a wide range of compositions by suitably varying the alimentation feed: up to 67 and 75 mol% of O and M incorporated for poly(ocimene-butadiene) and poly(myrcene-butadiene) copolymers, respectively. These new materials with elastomeric properties (glass transition temperatures observed in the range of −5.7 to −72.5 °C) were fully characterized by differential scanning calorimetry, size exclusion chromatography, and nuclear magnetic resonance spectroscopy (1H, 13C, and two-dimensional experiments).
David Hermann Lamparelli; Veronica Paradiso; Carmine Capacchione. NEW ELASTOMERIC MATERIALS FROM BIOMASS: STEREOSELECTIVE POLYMERIZATION OF LINEAR TERPENES AND THEIR COPOLYMERIZATION WITH BUTADIENE BY USING A COBALT COMPLEX WITH PHOSPHANE LIGANDS. Rubber Chemistry and Technology 2020, 93, 605 -614.
AMA StyleDavid Hermann Lamparelli, Veronica Paradiso, Carmine Capacchione. NEW ELASTOMERIC MATERIALS FROM BIOMASS: STEREOSELECTIVE POLYMERIZATION OF LINEAR TERPENES AND THEIR COPOLYMERIZATION WITH BUTADIENE BY USING A COBALT COMPLEX WITH PHOSPHANE LIGANDS. Rubber Chemistry and Technology. 2020; 93 (4):605-614.
Chicago/Turabian StyleDavid Hermann Lamparelli; Veronica Paradiso; Carmine Capacchione. 2020. "NEW ELASTOMERIC MATERIALS FROM BIOMASS: STEREOSELECTIVE POLYMERIZATION OF LINEAR TERPENES AND THEIR COPOLYMERIZATION WITH BUTADIENE BY USING A COBALT COMPLEX WITH PHOSPHANE LIGANDS." Rubber Chemistry and Technology 93, no. 4: 605-614.
Coupling of CO2 with epoxides is a green emerging alternative for the synthesis of cyclic organic carbonates (COC) and aliphatic polycarbonates (APC). The scope of this work is to provide a comprehensive overview of metal complexes having sulfur-containing ligands as homogeneous catalytic systems able to efficiently promote this transformation with a concise discussion of the most significant results. The crucial role of sulfur as the hemilabile ligand and its influence on the catalytic activity are highlighted as well.
Veronica Paradiso; Vito Capaccio; David Hermann Lamparelli; Carmine Capacchione. Metal Complexes Bearing Sulfur-Containing Ligands as Catalysts in the Reaction of CO2 with Epoxides. Catalysts 2020, 10, 825 .
AMA StyleVeronica Paradiso, Vito Capaccio, David Hermann Lamparelli, Carmine Capacchione. Metal Complexes Bearing Sulfur-Containing Ligands as Catalysts in the Reaction of CO2 with Epoxides. Catalysts. 2020; 10 (8):825.
Chicago/Turabian StyleVeronica Paradiso; Vito Capaccio; David Hermann Lamparelli; Carmine Capacchione. 2020. "Metal Complexes Bearing Sulfur-Containing Ligands as Catalysts in the Reaction of CO2 with Epoxides." Catalysts 10, no. 8: 825.
Theranostics based on two-photon excitation of therapeutics in the NIR region is an emerging and powerful tool in cancer therapy since this radiation deeply penetrates healthy biological tissues and produces selective cell death. Aggregates of gold nanoparticles coated with glutathione corona functionalized with the dansyl chromophore (a-DG-AuNPs) were synthesized and found efficient nanodevice for applications in photothermal therapy (PTT). Actually the nanoparticle aggregation enhances the quenching of radiative excitation and the consequent conversion into heat. The a-DG-AuNPs are readily internalized in Hep G2 where the chromophore acts as both antenna and transducer of the NIR radiation under two-photons excitation, determining efficient cell ablation via photothermal effect.
Antonio Buonerba; Rosita Lapenta; Anna Donniacuo; Magda Licasale; Elena Vezzoli; Stefano Milione; Carmine Capacchione; Mario Felice Tecce; Andrea Falqui; Roberto Piacentini; Claudio Grassi; Alfonso Grassi. NIR multiphoton ablation of cancer cells, fluorescence quenching and cellular uptake of dansyl-glutathione-coated gold nanoparticles. Scientific Reports 2020, 10, 1 -14.
AMA StyleAntonio Buonerba, Rosita Lapenta, Anna Donniacuo, Magda Licasale, Elena Vezzoli, Stefano Milione, Carmine Capacchione, Mario Felice Tecce, Andrea Falqui, Roberto Piacentini, Claudio Grassi, Alfonso Grassi. NIR multiphoton ablation of cancer cells, fluorescence quenching and cellular uptake of dansyl-glutathione-coated gold nanoparticles. Scientific Reports. 2020; 10 (1):1-14.
Chicago/Turabian StyleAntonio Buonerba; Rosita Lapenta; Anna Donniacuo; Magda Licasale; Elena Vezzoli; Stefano Milione; Carmine Capacchione; Mario Felice Tecce; Andrea Falqui; Roberto Piacentini; Claudio Grassi; Alfonso Grassi. 2020. "NIR multiphoton ablation of cancer cells, fluorescence quenching and cellular uptake of dansyl-glutathione-coated gold nanoparticles." Scientific Reports 10, no. 1: 1-14.
In this work we present a green synthetic pathway for the obtaining of bio-surfactants derived from glycerol. By extending a Lewis acid catalyzed reaction between glycidol and primary alcohols we obtained good conversion to the desired monoalkylglycidyl ether (MAGE) for long chain alcohols (n-octanol, n-decanol and n-dodecanol) reaching initial turnover frequency TOF up to 2633 h−1in the case of octanol. The obtained MAGEs were fully characterized and the critical micelle concentration (CMC) was determined for all bio-surfactants using a spectrophotometric approach such as pyrene method with peak difference (P2–P7) linear fitting (octylglyceryl ether: 0.97 ± 0.02 mM; decylglyceryl ether: 0.85 ± 0.03 mM; dodecylglyceryl ether: 0.71 ± 0.04 mM).
Maria Ricciardi; Raffaele Cucciniello; Joel Barrault; Antonio Faggiano; Carmine Capacchione; Antonio Proto. A step towards bio-surfactants: Monoalkylglyceryl ethers synthesis through glycidol alcoholysis with long-chain alcohols catalyzed by Al(OTf)3. Sustainable Chemistry and Pharmacy 2020, 17, 100281 .
AMA StyleMaria Ricciardi, Raffaele Cucciniello, Joel Barrault, Antonio Faggiano, Carmine Capacchione, Antonio Proto. A step towards bio-surfactants: Monoalkylglyceryl ethers synthesis through glycidol alcoholysis with long-chain alcohols catalyzed by Al(OTf)3. Sustainable Chemistry and Pharmacy. 2020; 17 ():100281.
Chicago/Turabian StyleMaria Ricciardi; Raffaele Cucciniello; Joel Barrault; Antonio Faggiano; Carmine Capacchione; Antonio Proto. 2020. "A step towards bio-surfactants: Monoalkylglyceryl ethers synthesis through glycidol alcoholysis with long-chain alcohols catalyzed by Al(OTf)3." Sustainable Chemistry and Pharmacy 17, no. : 100281.
Sustainable lactams, which are derived from terpenes, are used for the synthesis of different novel copolymers via ring‐opening polymerization. Different conditions are tested and the incorporation of the different monomers into the polymers is elucidated. This gives access to a variety of new polymer structures and their application range is thus remarkably extended.
Malte Winnacker; David Hermann Lamparelli; Carmine Capacchione; Hicran H. Güngör; Lucas Stieglitz; Katia S. Rodewald; Matthias Schmidt; Thomas F. Gronauer. Sustainable Polyesteramides and Copolyamides: Insights into the Copolymerization Behavior of Terpene‐Based Lactams. Macromolecular Chemistry and Physics 2020, 221, 1 .
AMA StyleMalte Winnacker, David Hermann Lamparelli, Carmine Capacchione, Hicran H. Güngör, Lucas Stieglitz, Katia S. Rodewald, Matthias Schmidt, Thomas F. Gronauer. Sustainable Polyesteramides and Copolyamides: Insights into the Copolymerization Behavior of Terpene‐Based Lactams. Macromolecular Chemistry and Physics. 2020; 221 (12):1.
Chicago/Turabian StyleMalte Winnacker; David Hermann Lamparelli; Carmine Capacchione; Hicran H. Güngör; Lucas Stieglitz; Katia S. Rodewald; Matthias Schmidt; Thomas F. Gronauer. 2020. "Sustainable Polyesteramides and Copolyamides: Insights into the Copolymerization Behavior of Terpene‐Based Lactams." Macromolecular Chemistry and Physics 221, no. 12: 1.
The copolymerization of renewable monomers such as ocimene (O), myrcene (M), and farnesene (F) with butadiene (B), promoted by dichloro{1,4-dithiabutanediyl-2,2′-bis[4,6-bis(2-phenyl-2-propyl)phenoxy]}titanium (1) activated by modified methylalumoxane (m-MAO) under mild reaction conditions, was investigated. Copolymers in a wide range of compositions were obtained through a judicious control of the alimentation feed (up to 85% of terpene incorporated in the case of poly(ocimene–butadiene) (POB)). Analysis of POB, poly(myrcene–butadiene) (PMB), and poly(farnesene–butadiene) (PFB) microstructures revealed the good stereoselectivity of 1, both in the butadiene (up to 95%) and in the terpene (up to 92%, 71%, and 86% for O, M, and F, respectively) insertion. For all these new materials, a complete 13C NMR assignment was performed, revealing a multiblock structure. A sample of POB was also evaluated as a component in a model tread compound leading to improved mechanical properties with respect to the corresponding plain butadiene rubbers.
David Hermann Lamparelli; Veronica Paradiso; Francesco Della Monica; Antonio Proto; Silvia Guerra; Luca Giannini; Carmine Capacchione. Toward More Sustainable Elastomers: Stereoselective Copolymerization of Linear Terpenes with Butadiene. Macromolecules 2020, 53, 1665 -1673.
AMA StyleDavid Hermann Lamparelli, Veronica Paradiso, Francesco Della Monica, Antonio Proto, Silvia Guerra, Luca Giannini, Carmine Capacchione. Toward More Sustainable Elastomers: Stereoselective Copolymerization of Linear Terpenes with Butadiene. Macromolecules. 2020; 53 (5):1665-1673.
Chicago/Turabian StyleDavid Hermann Lamparelli; Veronica Paradiso; Francesco Della Monica; Antonio Proto; Silvia Guerra; Luca Giannini; Carmine Capacchione. 2020. "Toward More Sustainable Elastomers: Stereoselective Copolymerization of Linear Terpenes with Butadiene." Macromolecules 53, no. 5: 1665-1673.
A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO 2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers .
Francesco Della Monica; Veronica Paradiso; Alfonso Grassi; Stefano Milione; Luigi Cavallo; Carmine Capacchione. A Novel [OSSO]‐Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides. Chemistry – A European Journal 2020, 26, 5347 -5353.
AMA StyleFrancesco Della Monica, Veronica Paradiso, Alfonso Grassi, Stefano Milione, Luigi Cavallo, Carmine Capacchione. A Novel [OSSO]‐Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides. Chemistry – A European Journal. 2020; 26 (24):5347-5353.
Chicago/Turabian StyleFrancesco Della Monica; Veronica Paradiso; Alfonso Grassi; Stefano Milione; Luigi Cavallo; Carmine Capacchione. 2020. "A Novel [OSSO]‐Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides." Chemistry – A European Journal 26, no. 24: 5347-5353.
The efficient formation of cyclic polyesters from the ring-opening polymerization of lactide, ϵ-caprolactone, and β-butyrolactone catalyzed by a 1,4-dithiabutanedyl-2,2'-bis(4,6-dicumylphenol) [OSSO]-FeCl complex activated with cyclohexene oxide was achieved. The catalyst was very active (initial turnover frequency up to 2718 h-1 ), robust, and worked with a monomer/Fe ratio up to 10 000. The formation of cyclic polymers was supported by using high-resolution matrix-assisted laser desorption ionization (MALDI) MS, and the average ring size (≈5 kDa for cyclic polylactide) independent of the reaction conditions. A monometallic ring-opening polymerization/cyclization mechanism was proposed from the results of a kinetic investigation.
Salvatore Impemba; Francesco Della Monica; Alfonso Grassi; Carmine Capacchione; Stefano Milione; Impemba Salvatore. Cyclic Polyester Formation with an [OSSO]‐Type Iron(III) Catalyst. ChemSusChem 2019, 13, 141 -145.
AMA StyleSalvatore Impemba, Francesco Della Monica, Alfonso Grassi, Carmine Capacchione, Stefano Milione, Impemba Salvatore. Cyclic Polyester Formation with an [OSSO]‐Type Iron(III) Catalyst. ChemSusChem. 2019; 13 (1):141-145.
Chicago/Turabian StyleSalvatore Impemba; Francesco Della Monica; Alfonso Grassi; Carmine Capacchione; Stefano Milione; Impemba Salvatore. 2019. "Cyclic Polyester Formation with an [OSSO]‐Type Iron(III) Catalyst." ChemSusChem 13, no. 1: 141-145.
Dirong Gong; Weilun Ying; Junyi Zhao; Wenxin Li; Yuechao Xu; Yunjie Luo; Xuequan Zhang; Carmine Capacchione; Alfonso Grassi. Controlling external diphenylcyclohexylphosphine feeding to achieve cis-1,4-syn-1,2 sequence controlled polybutadienes via cobalt catalyzed 1,3-butadiene polymerization. Journal of Catalysis 2019, 377, 367 -377.
AMA StyleDirong Gong, Weilun Ying, Junyi Zhao, Wenxin Li, Yuechao Xu, Yunjie Luo, Xuequan Zhang, Carmine Capacchione, Alfonso Grassi. Controlling external diphenylcyclohexylphosphine feeding to achieve cis-1,4-syn-1,2 sequence controlled polybutadienes via cobalt catalyzed 1,3-butadiene polymerization. Journal of Catalysis. 2019; 377 ():367-377.
Chicago/Turabian StyleDirong Gong; Weilun Ying; Junyi Zhao; Wenxin Li; Yuechao Xu; Yunjie Luo; Xuequan Zhang; Carmine Capacchione; Alfonso Grassi. 2019. "Controlling external diphenylcyclohexylphosphine feeding to achieve cis-1,4-syn-1,2 sequence controlled polybutadienes via cobalt catalyzed 1,3-butadiene polymerization." Journal of Catalysis 377, no. : 367-377.
A new Fe(III)‐triflate complex, bearing a bis‐thioether‐di‐phenolate [OSSO]‐type ligand, is reported to promote the ring‐opening of glycidol with alcohols under mild reaction conditions (0.05 mol% of catalyst and 80 °C). The reaction proceeds with high activity (initial turnover frequency of 1680 h‐1 for ethanol) and selectivity (>95%) toward the formation of twelve monoalkyl glyceryl ethers (MAGEs) in a regioselective fashion (84‐96% of non‐symmetric regioisomer). This synthetic approach allows the conversion of a glycerol‐derived platform molecule, such as glycidol, to high value‐added products using an Earth‐crust abundant metal‐based catalyst.
Francesco Della Monica; Maria Ricciardi; Antonio Proto; Raffaele Cucciniello; Carmine Capacchione. Regioselective Ring‐Opening of Glycidol to Monoalkyl Glyceryl Ethers Promoted by an [OSSO]‐Fe III Triflate Complex. ChemSusChem 2019, 12, 3448 -3452.
AMA StyleFrancesco Della Monica, Maria Ricciardi, Antonio Proto, Raffaele Cucciniello, Carmine Capacchione. Regioselective Ring‐Opening of Glycidol to Monoalkyl Glyceryl Ethers Promoted by an [OSSO]‐Fe III Triflate Complex. ChemSusChem. 2019; 12 (15):3448-3452.
Chicago/Turabian StyleFrancesco Della Monica; Maria Ricciardi; Antonio Proto; Raffaele Cucciniello; Carmine Capacchione. 2019. "Regioselective Ring‐Opening of Glycidol to Monoalkyl Glyceryl Ethers Promoted by an [OSSO]‐Fe III Triflate Complex." ChemSusChem 12, no. 15: 3448-3452.
The thin film morphology of stereoregular syndiotactic poly(p‐methylstyrene)‐cis‐1,4‐polybutadiene [sP(pMS‐B)] multiblock copolymers has been investigated by tapping mode atomic force microscopy (TM‐AFM) at variance of the polymer composition and monomer block lengths. The morphology of the thin films ranges from isolated circular domains of sP(pMS) embedded into a matrix of polybutadiene (PB) to isolated domain of PB embedded into a matrix of sP(pMS), passing through bicontinuous (jagged) lamellae when the p‐methylstyrene (pMS) concentration is in the range 20‐67 mol%. Multiple folding of the polymer segments, where i.e. polymer segments to each other phase are able to generate greater domain, has been postulated and validated by considerations on the polymer architecture, the thermal and crystalline behaviour. This article is protected by copyright. All rights reserved.
Antonio Buonerba; Francesco Della Monica; Vito Speranza; Carmine Capacchione; Stefano Milione; Alfonso Grassi. Thin‐film nanostructure and polymer architecture in semicrystalline syndiotactic poly( p ‐methylstyrene)–( cis ‐1,4‐polybutadiene) multiblock copolymers. Polymer International 2019, 68, 1681 -1687.
AMA StyleAntonio Buonerba, Francesco Della Monica, Vito Speranza, Carmine Capacchione, Stefano Milione, Alfonso Grassi. Thin‐film nanostructure and polymer architecture in semicrystalline syndiotactic poly( p ‐methylstyrene)–( cis ‐1,4‐polybutadiene) multiblock copolymers. Polymer International. 2019; 68 (10):1681-1687.
Chicago/Turabian StyleAntonio Buonerba; Francesco Della Monica; Vito Speranza; Carmine Capacchione; Stefano Milione; Alfonso Grassi. 2019. "Thin‐film nanostructure and polymer architecture in semicrystalline syndiotactic poly( p ‐methylstyrene)–( cis ‐1,4‐polybutadiene) multiblock copolymers." Polymer International 68, no. 10: 1681-1687.
The zirconium complexes (OSSOCl)ZrOtBu2 (1), (OSSOBr)ZrOtBu2 (2) and (OSSOtBu)ZrOtBu2 (3) bearing OSSO-type ligands (OSSOCl-H = 1,4-dithiabutanedyl-2,2′-bis(4,6-dichlorophenol); OSSOBr-H = 1,4-dithiabutanedyl-2,2′-bis(4,6-dibromophenol); OSSOtBu-H = 1,4-dithiabutanedyl-2,2′-bis(4,6-di-tert-butyl-phenol)) were prepared and characterized. NMR spectroscopy revealed a rigid octahedral coordination geometry with a facial-facial coordination of the [OSSO] ligand to the metal complex. These compounds were active in the ring-opening polymerization of l-lactide exerting an effective control over the polymerization reaction. Activities correlated with the electron-withdrawing character of the ortho and para groups of the OSSO ligands. Density functional theory (DFT) investigations indicated that substitution with increasingly electron-withdrawing groups favors the monomer coordination and determines an earlier, more reactive transition state.
Angelo Meduri; Mina Mazzeo; Marina Lamberti; Carmine Capacchione; Stefano Milione. Electronic influence of ligand substituents in the ring-opening polymerization of l-Lactide promoted by OSSO-type zirconium complexes. Molecular Catalysis 2019, 471, 54 -59.
AMA StyleAngelo Meduri, Mina Mazzeo, Marina Lamberti, Carmine Capacchione, Stefano Milione. Electronic influence of ligand substituents in the ring-opening polymerization of l-Lactide promoted by OSSO-type zirconium complexes. Molecular Catalysis. 2019; 471 ():54-59.
Chicago/Turabian StyleAngelo Meduri; Mina Mazzeo; Marina Lamberti; Carmine Capacchione; Stefano Milione. 2019. "Electronic influence of ligand substituents in the ring-opening polymerization of l-Lactide promoted by OSSO-type zirconium complexes." Molecular Catalysis 471, no. : 54-59.
Francesco Della Monica; Antonio Buonerba; Carmine Capacchione. Homogeneous Iron Catalysts in the Reaction of Epoxides with Carbon Dioxide. Advanced Synthesis & Catalysis 2018, 361, 265 -282.
AMA StyleFrancesco Della Monica, Antonio Buonerba, Carmine Capacchione. Homogeneous Iron Catalysts in the Reaction of Epoxides with Carbon Dioxide. Advanced Synthesis & Catalysis. 2018; 361 (2):265-282.
Chicago/Turabian StyleFrancesco Della Monica; Antonio Buonerba; Carmine Capacchione. 2018. "Homogeneous Iron Catalysts in the Reaction of Epoxides with Carbon Dioxide." Advanced Synthesis & Catalysis 361, no. 2: 265-282.
A new [OSSO]‐Fe(III) metallate complex was prepared and characterized. We demonstrated that such metallate is the real catalytic active species for the cycloaddition of CO2 to the epoxides, formed from the in situ reaction of the related [OSSO‐]Fe(III) neutral complexes and tetrabutylammonium bromide. The metallate complex was used as a single component catalyst for the formation of cyclic organic carbonates from ten epoxides and CO2 at 1 bar pressure with good activity.
Francesco Della Monica; Antonio Buonerba; Veronica Paradiso; Stefano Milione; Alfonso Grassi; Carmine Capacchione. [OSSO]-Type Fe(III) Metallate as Single-Component Catalyst for the CO2 Cycloaddition to Epoxides. Advanced Synthesis & Catalysis 2018, 361, 283 -288.
AMA StyleFrancesco Della Monica, Antonio Buonerba, Veronica Paradiso, Stefano Milione, Alfonso Grassi, Carmine Capacchione. [OSSO]-Type Fe(III) Metallate as Single-Component Catalyst for the CO2 Cycloaddition to Epoxides. Advanced Synthesis & Catalysis. 2018; 361 (2):283-288.
Chicago/Turabian StyleFrancesco Della Monica; Antonio Buonerba; Veronica Paradiso; Stefano Milione; Alfonso Grassi; Carmine Capacchione. 2018. "[OSSO]-Type Fe(III) Metallate as Single-Component Catalyst for the CO2 Cycloaddition to Epoxides." Advanced Synthesis & Catalysis 361, no. 2: 283-288.
The dichloro titanium complexes (OSSO tBu)TiCl2 (1) and (OSSOCum)TiCl2 (2) bearing o-phenylene-bridged OSSO-type ligands [OSSO tBu-H = 6,6'-((1,2-phenylenebis(sulfanediyl))bis(methylene))bis(2,4-di-tert-butyphenol) and OSSOCum-H = 6,6'-((1,2-phenylenebis(sulfanediyl))bis(methylene))bis(2,4-bis(2-phenylpropan-2-yl)phenol)] were prepared and characterized. The X-ray structure of 1 revealed that Ti atom has an octahedral coordination geometry with an fac-fac wrapping of the [OSSO] ligand. In solution at 25 °C, 1 mainly retains the C2 symmetric structure, whereas 2 shows an equilibrium between C2- and C1-symmetric stereoisomers. Activation of 2 with (Ph3C)[B(C6F5)4] led to a highly active catalytic system with an activity of 238 kgPE·molcat-1·bar-1·h-1; linear polyethylene with a Tm of 122 °C and Mw of 107 kDa were obtained under these conditions. Catalyst 1 displayed the moderate activity of 59 kgPE·molcat-1·bar-1·h-1. Gel permeation chromatography analysis revealed the formation of high-molecular-weight polyethylenes with very large distributions of the molecular weights, indicating a low control of the polymerization process, probably becaue of the presence of different active species in solution. Density functional theory investigation provides a rational for the relative high-molecular-weight polymers obtained with these complexes. The precatalyst 2 was also active in propylene polymerization producing atactic oligomers terminated with unsaturated end groups.
Rosita Lapenta; Antonio Buonerba; Ermanno Luciano; Francesco Della Monica; Assunta De Nisi; Magda Monari; Alfonso Grassi; Carmine Capacchione; Stefano Milione. Phenylene-Bridged OSSO-Type Titanium Complexes in the Polymerization of Ethylene and Propylene. ACS Omega 2018, 3, 11608 -11616.
AMA StyleRosita Lapenta, Antonio Buonerba, Ermanno Luciano, Francesco Della Monica, Assunta De Nisi, Magda Monari, Alfonso Grassi, Carmine Capacchione, Stefano Milione. Phenylene-Bridged OSSO-Type Titanium Complexes in the Polymerization of Ethylene and Propylene. ACS Omega. 2018; 3 (9):11608-11616.
Chicago/Turabian StyleRosita Lapenta; Antonio Buonerba; Ermanno Luciano; Francesco Della Monica; Assunta De Nisi; Magda Monari; Alfonso Grassi; Carmine Capacchione; Stefano Milione. 2018. "Phenylene-Bridged OSSO-Type Titanium Complexes in the Polymerization of Ethylene and Propylene." ACS Omega 3, no. 9: 11608-11616.