GIORGIO CAPOCASA

PhD Graduate

PhD program:: XXXIII


supervisor: Prof. Stefano Di Stefano

Thesis title: A supramolecular approach to hydrocarbon functionalization

Transition metal-based catalysis of C-H oxidation is quickly becoming a viable route for hydrocarbon functionalization. The possibilities for Organic Synthesis are exciting: new transformations are now available to the Chemist to design more elegant syntheses and to generate huge libraries of molecules through late-stage functionalization. However, that of selectivity is still a largely unsolved problem: for particular combinations of substrates and catalytic systems, steric and electronic effects can direct the oxidation on few specific sites but, in most cases, mixtures of products are formed. Supramolecular chemistry studies the interactions between distinct molecules. This branch of chemistry has found application in the development of catalysts that can recognize their substrate and orient it in such a way as to enhance the reactivity and selectivity of the catalytic system. The supramolecular approach can be defined as biomimetic; indeed, enzymes employ supramolecular interactions with their substrates to achieve their paradigmatic selectivity. This thesis explores the application of supramolecular recognition to hydrocarbon functionalization: a successful supramolecular system for C-H oxidation is studied in detail, then an attempt at designing a new imine-based supramolecular catalyst is made. Finally, a UV-Vis/XAS coupled technique is developed and the analysis of time-resolved XAS data is used for the first time to follow the reactions between a non-heme iron-oxo complex and various substrates to determine their rate constants.

Research products

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
paper: 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)

11573/1670870 - 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
paper: 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 (9)

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
paper: RSC ADVANCES (London: Royal Society of Chemistry) pp. 537-542 - issn: 2046-2069 - wos: WOS:000614277900058 (2) - scopus: 2-s2.0-85100382836 (2)

11573/1563178 - 2021 - New horizons for catalysis disclosed by supramolecular chemistry
Olivo, Giorgio; Capocasa, Giorgio; Del Giudice, Daniele; Lanzalunga, Osvaldo; Di Stefano, Stefano - 01g Articolo di rassegna (Review)
paper: CHEMICAL SOCIETY REVIEWS (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 7681-7724 - issn: 0306-0012 - wos: WOS:000651871700001 (98) - scopus: 2-s2.0-85109216445 (99)

11573/1603366 - 2021 - Insights into the Structure of Reaction Intermediates Through Coupled X-ray Absorption/UV-Vis Spectroscopy
Tavani, F.; Martini, A.; Sessa, F.; Capocasa, G.; Olivo, G.; Lanzalunga, O.; Di Stefano, Stefano; D'angelo, P. - 04b Atto di convegno in volume
conference: Meeting of the Italian Synchrotron Radiation Society, SILS 2019 (ita)
book: Springer Proceedings in Physics - (978-3-030-72004-9; 978-3-030-72005-6)

11573/1476321 - 2021 - Direct structural and mechanistic insights into fast bimolecular chemical reactions in solution through a coupled XAS/UV-Vis multivariate statistical analysis
Tavani, Francesco; Capocasa, Giorgio; Martini, Andrea; Sessa, Francesco; Di Stefano, Stefano; Lanzalunga, Osvaldo; D'angelo, Paola - 01a Articolo in rivista
paper: DALTON TRANSACTIONS (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 131-142 - issn: 1477-9226 - wos: WOS:000605666100014 (8) - scopus: 2-s2.0-85098985805 (9)

11573/1490551 - 2021 - Activation of C-H bonds by a nonheme iron(iv)-oxo complex: mechanistic evidence through a coupled EDXAS/UV-Vis multivariate analysis
Tavani, Francesco; Capocasa, Giorgio; Martini, Andrea; Sessa, Francesco; Di Stefano, Stefano; Lanzalunga, Osvaldo; D'angelo, Paola - 01a Articolo in rivista
paper: PHYSICAL CHEMISTRY CHEMICAL PHYSICS (Thomas Graham House, Science Park, Cambridge: Royal Society of Chemistry) pp. 1188-1196 - issn: 1463-9076 - wos: WOS:000610150200041 (7) - scopus: 2-s2.0-85100039889 (9)

11573/1486200 - 2021 - Insight into the chemoselective aromatic vs. side-chain hydroxylation of alkylaromatics with H2O2 catalyzed by a non-heme imine-based iron complex
Ticconi, B.; Capocasa, G.; Cerrato, A.; Di Stefano, Stefano; Lapi, A.; Marincioni, B.; Olivo, G.; Lanzalunga, O. - 01a Articolo in rivista
paper: CATALYSIS SCIENCE & TECHNOLOGY (Cambridge : Royal Society of Chemistry, 2011-) pp. 171-178 - issn: 2044-4753 - wos: WOS:000609012400013 (4) - scopus: 2-s2.0-85099725038 (5)

11573/1409346 - 2020 - Controlling the liberation rate of the in situ release of a chemical fuel for the operationally autonomous motions of molecular machines
Biagini, Chiara; Capocasa, Giorgio; Del Giudice, Daniele; Cataldi, Valerio; Mandolini, Luigi; Di Stefano, Stefano - 01a Articolo in rivista
paper: ORGANIC & BIOMOLECULAR CHEMISTRY (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 3867-3873 - issn: 1477-0520 - wos: WOS:000537137600011 (11) - scopus: 2-s2.0-85085586056 (11)

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
paper: 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)

11573/1414525 - 2020 - Supramolecular catalysts featuring crown ethers as recognition units
Di Stefano, Stefano; Capocasa, G.; Mandolini, L. - 01a Articolo in rivista
paper: 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. 3340-3350 - issn: 1434-193X - wos: WOS:000517496500001 (24) - scopus: 2-s2.0-85080974009 (23)

11573/1409358 - 2020 - Predictable selectivity in remote C-H oxidation of steroids: analysis of substrate binding mode
Olivo, Giorgio; Capocasa, Giorgio; Ticconi, Barbara; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel - 01a Articolo in rivista
paper: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION (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. 12703-12708 - issn: 1433-7851 - wos: WOS:000533986300001 (31) - scopus: 2-s2.0-85085546717 (31)

11573/1438571 - 2020 - Direct Mechanistic Evidence for a Nonheme Complex Reaction through a Multivariate XAS Analysis
Tavani, F.; Martini, A.; Capocasa, G.; Di Stefano, Stefano; Lanzalunga, O.; D'angelo, P. - 01a Articolo in rivista
paper: INORGANIC CHEMISTRY (Washington, DC: American Chemical Society) pp. 9979-9989 - issn: 0020-1669 - wos: WOS:000552287100052 (10) - scopus: 2-s2.0-85087640152 (13)

11573/1335555 - 2019 - The hydrolysis of the anhydride of 2-cyano-2-phenylpropanoic acid triggers the repeated back and forth motions of an acid–base operated molecular switch
Biagini, C.; Capocasa, G.; Cataldi, V.; Del Giudice, D.; Mandolini, L.; Di Stefano, Stefano - 01a Articolo in rivista
paper: 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. 15205-15211 - issn: 0947-6539 - wos: WOS:000493849200001 (19) - scopus: 2-s2.0-85074786690 (21)

11573/1236047 - 2019 - Coupled X-ray absorption/UV-vis monitoring of fast oxidation reactions involving a nonheme Iron-Oxo complex
Capocasa, Giorgio; Sessa, Francesco; Tavani, Francesco; Monte, Manuel; Olivo, Giorgio; Pascarelli, Sakura; Lanzalunga, Osvaldo; Di Stefano, Stefano; D'angelo, Paola - 01a Articolo in rivista
paper: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Washington, DC : American Chemical Society, 1879-) pp. 2299-2304 - issn: 1520-5126 - wos: WOS:000459222100021 (25) - scopus: 2-s2.0-85061493425 (26)

11573/1219542 - 2019 - Enzyme-like substrate-selectivity in C-H oxidation enabled by recognition
Olivo, Giorgio; Capocasa, Giorgio; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel - 01a Articolo in rivista
paper: CHEMICAL COMMUNICATIONS (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 917-920 - issn: 1359-7345 - wos: WOS:000457296200003 (33) - scopus: 2-s2.0-85060173136 (37)

11573/1039574 - 2017 - Direct hydroxylation of benzene and aromatics with H2O2 catalyzed by a self-assembled iron complex: evidence for a metal-based mechanism
Capocasa, Giorgio; Olivo, Giorgio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano - 01a Articolo in rivista
paper: CATALYSIS SCIENCE & TECHNOLOGY (Cambridge : Royal Society of Chemistry, 2011-) pp. 5677-5686 - issn: 2044-4753 - wos: WOS:000417706600024 (31) - scopus: 2-s2.0-85036454463 (32)

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