FEDERICO FRATELORETO

Dottore di ricerca

ciclo: XXXV


supervisore: Stefano Di Stefano

Titolo della tesi: Supramolecular systems involving transition metals: catalysis and translocation

Herein I report the results of the research work I carried out during my PhD. I mainly focused on two aspects of supramolecular systems involving transition metals: catalysis and translocation. Concerning catalysis, I worked on a supramolecular approach to C–H bond oxidation using non-heme metal complexes as catalysts. The outcomes of such research are presented in the first three chapters of this thesis. In Chapters 1 and 2 a family of bis-imino, self-assembled supramolecular non heme iron catalysts active in C–H bond oxidation is illustrated. The possibility to achieve selective oxidation of aromatic and aliphatic substrates has been explored by decorating the ligand scaffold of the self-assembled iron complexes with supramolecular receptors (Chapter 1) or with sterically hindered groups (Chapter 2). In the first case, the catalyst endowed with benzo 18 crown 6 receptor units showed site selectivity toward aromatic oxidation, but such property seemed to be not entirely ascribable to supramolecular recognition. In the second case, the insertion of large and sterically demanding groups on the catalyst backbone did not lead to the insurgence of steric effects on the catalyzed reaction. However, such findings reinforced a mechanistic hypothesis previously reported for analogous catalysts. Chapter 3 reports the preliminary results of a project carried out during my stay to the University of Girona under the supervision of Professor Miquel Costas. This project aims to exploit supramolecular self-assembly to provide with a recognition unit an already-known catalytically active iron (or manganese) complex. To do this, two receptor-bearing carboxylic acids have been synthesized. The carboxylic acid moiety will hopefully be able to bind to the metal center of the catalyst, providing it with the supramolecular receptor. The last two chapters concerns translocation processes of transition metal ions. Chapter 4 reports the reduction promoted by an activated carboxylic acid of the octahedral Cu2+ - terpyridine complex, to the tetrahedral Cu+ - neocuproine complex. In Chapter 5 the dissipative back-and-forth translocation of the Zn2+ ion between hexaaza 18 crown 6 and two terpyridine moieties, is described. For the investigation of both translocation processes, a combination of X-ray absorption and proton nuclear magnetic resonance spectroscopies with multivariate curve resolution analysis has been exploited in order to understand the concentration-time evolution of all relevant inorganic and organic species involved in the reactions.

Produzione scientifica

11573/1701952 - 2023 - Signal Transduction Allows Temporal Control of the Potential of a Concentration Cell Driven by the Decarboxylation of an Activated Carboxylic Acid
Capocasa, Giorgio; Frateloreto, Federico; Cavallari, Stefania Correale; Valentini, Matteo; Lanzalunga, Osvaldo; Di Stefano, Stefano - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 0947-6539 - wos: WOS:001157373500001 (0) - scopus: 2-s2.0-85184435132 (0)

11573/1685374 - 2023 - Kinetic and Product Study of the S-oxidation vs HAT Chemoselectivity in Reactions Promoted by Nonheme Iron(IV)-oxo Complex/NHPI Mediator System
Di Berto Mancini, M.; Bernardini, M.; Emanuel Birzu, B.; De Santis, A.; Di Stefano, Stefano; Frateloreto, F.; Khaksar, D.; Lapi, A.; Olivo, G.; Lanzalunga, O. - 01a Articolo in rivista
rivista: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 1434-193X - wos: WOS:001031621400001 (0) - scopus: 2-s2.0-85164457925 (0)

11573/1677337 - 2023 - Cyclization reactions in confined space
Spatola, E.; Frateloreto, F.; Del Giudice, D.; Olivo, G.; Di Stefano, Stefano - 01g Articolo di rassegna (Review)
rivista: CURRENT OPINION IN COLLOID & INTERFACE SCIENCE (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. - - issn: 1359-0294 - wos: WOS:000962503700001 (0) - scopus: 2-s2.0-85150855057 (0)

11573/1691319 - 2023 - Combining X-ray Absorption and NMR spectroscopies to investigate a chemical reaction in solution
Tavani, Francesco; Del Giudice, Daniele; Di Berto Mancini, Marika; Frateloreto, Federico; Busato, Matteo; Lanzalunga, Osvaldo; Di Stefano, Stefano; D’Angelo, Paola - 01a Articolo in rivista
rivista: RADIATION PHYSICS AND CHEMISTRY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 111199-1-111199-6 - issn: 0969-806X - wos: (0) - scopus: 2-s2.0-85168825418 (0)

11573/1686570 - 2023 - A Doubly Dissipative System Driven by Chemical and Radiative Stimuli
Valentini, Matteo; Frateloreto, Federico; Conti, Matteo; Cacciapaglia, Roberta; Del Giudice, Daniele; Di Stefano, Stefano - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 0947-6539 - wos: WOS:001037834300001 (1) - scopus: 2-s2.0-85165990942 (0)

11573/1652783 - 2022 - Chemical Tools for the Temporal Control of Water Solution pH and Applications in Dissipative Systems
Del Giudice, D.; Frateloreto, F.; Sappino, C.; Di Stefano, Stefano - 01a Articolo in rivista
rivista: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (Weinheim : Wiley-VCH-Verl.) pp. - - issn: 1099-0690 - wos: WOS:000815356300001 (13) - scopus: 2-s2.0-85132577278 (9)

11573/1603364 - 2022 - Two Faces of the Same Coin: Coupling X-Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes
Del Giudice, D.; Tavani, F.; Di Berto Mancini, M.; Frateloreto, F.; Busato, M.; Oliveira De Souza, D.; Cenesi, F.; Lanzalunga, O.; Di Stefano, Stefano; D'angelo, P. - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 0947-6539 - wos: WOS:000730219700001 (8) - scopus: 2-s2.0-85121358737 (6)

11573/1670870 - 2022 - Following a Silent Metal Ion: A Combined X-ray Absorption and Nuclear Magnetic Resonance Spectroscopic Study of the Zn2+ Cation Dissipative Translocation between Two Different Ligands
Frateloreto, Federico; Tavani, Francesco; Di Berto Mancini, Marika; Del Giudice, Daniele; Capocasa, Giorgio; Kieffer, Isabelle; Lanzalunga, Osvaldo; Di Stefano, Stefano; D'angelo, Paola - 01a Articolo in rivista
rivista: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS (Washington, DC: American Chemical Society) pp. 5522-5529 - issn: 1948-7185 - wos: WOS:000819338000001 (7) - scopus: 2-s2.0-85133100528 (7)

11573/1582606 - 2021 - Change of Selectivity in C-H Functionalization Promoted by Nonheme Iron(IV)-oxo Complexes by the Effect of the N-hydroxyphthalimide HAT Mediator
Di Berto Mancini, M.; Del Gelsomino, A.; Di Stefano, Stefano; Frateloreto, F.; Lapi, A.; Lanzalunga, O.; Olivo, G.; Sajeva, S. - 01a Articolo in rivista
rivista: ACS OMEGA (Washington, D.C. : American Chemical Society, 2016-) pp. 26428-26438-26438 - issn: 2470-1343 - wos: WOS:000708560000051 (3) - scopus: 2-s2.0-85117484898 (5)

11573/1495076 - 2021 - Increasing the steric hindrance around the catalytic core of a self-assembled imine-based non-heme iron catalyst for C-H oxidation
Frateloreto, Federico; Capocasa, Giorgio; Olivo, Giorgio; Abdel Hady, Karm; Sappino, Carla; Di Berto Mancini, Marika; Levi Mortera, Stefano; Lanzalunga, Osvaldo; Di Stefano, Stefano - 01a Articolo in rivista
rivista: RSC ADVANCES (London: Royal Society of Chemistry) pp. 537-542 - issn: 2046-2069 - wos: WOS:000614277900058 (2) - scopus: 2-s2.0-85100382836 (2)

11573/1414508 - 2020 - Easy synthesis of a self-assembled imine-based iron(II) complex endowed with crown-ether receptors
Capocasa, G.; Di Berto Mancini, M.; Frateloreto, F.; Lanzalunga, O.; Olivo, G.; Di Stefano, Stefano - 01a Articolo in rivista
rivista: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. 3390-3397 - issn: 1434-193X - wos: WOS:000537715700001 (5) - scopus: 2-s2.0-85086006273 (5)

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