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Supervisors:  Prof. Pampaloni Guido

Title:  Synthesis, Structural Characterization and Catalytic Activity of Early Transition Metal Complexes in CO2 Activation Reactions.

Abstract: 

Carbon dioxide is regarded as an easily available and nontoxic C1 feedstock for the preparation of a large number of chemicals, but its relatively high chemical inertia requires an initial activation step. Hence, in the last years various catalysts have been studied for the conversion of CO2 into useful chemicals. My project is aimed to the synthesis, characterization and study of the catalytic activity of complexes based on nontoxic and inexpensive metal centers (e.g. Ti, Nb). Such complexes will be tested as catalysts in CO2 activation reactions with various substrates (e.g. epoxides, halohydrins, alcohols).

Publications:

“MoCl5 as an effective chlorinating agent towards α-amino acids: synthesis of α-ammonium-acylchloride salts and α-amino-acylchloride complexes”, M. Bortoluzzi, G. Bresciani, F. Marchetti, G. Pampaloni, S. Zacchini, Dalton Trans., 2015, 44(21), 1030-1037.

“Synthesis and study of the stability of amidinium/guanidinium carbamates of amines and α-amino acids”, L. Biancalana, G. Bresciani, C. Chiappe, F. Marchetti, G Pampaloni, New J. Chem. 2017, 41 (4), 1798-1805.

“Synthesis and structural characterization of mixed halide–N, N-diethylcarbamates of group 4 metals, including a case of unusual tetrahydrofuran activation”, M. Bortoluzzi, G. Bresciani, F. Marchetti, G. Pampaloni, S. Zacchini, New J. Chem. 2017, 41 (4), 1781-1789.

“Modifying bis(triflimide) ionic liquids by dissolving early transition metal carbamates”, L. Biancalana, G. Bresciani, C. Chiappe, F. Marchetti, G. Pampaloni, C. S. Pomelli, Phys.Chem.Chem.Phys , 2018, 20, 5057- 5066.

“Structural Characterization of a Fluorido-Amide of Niobium, and Facile CO2 Incorporation Affording a Fluorido-Carbamate” G. Bresciani, M. Bortoluzzi, S. Zacchini, F. Marchetti, G. Pampaloni, Eur. J. Inorg. Chem., 2018, 999–1006.

“Synthesis and Structural Characterization of Non-Homoleptic Carbamato Complexes of VV and WVI and Their Facile Implantation onto Silica Surfaces” G. Bresciani, M. Bortoluzzi, S. Zacchini, A. Gabbani, F. Pineider, F. Marchetti, G. Pampaloni Eur. J. Inorg. Chem., 2018, 1176–1184.

“Iron (III) N, N‐Dialkylcarbamates Catalyze the Formation of Cyclic Carbonates from Carbon Dioxide and Epoxides at Ambient Conditions via Dynamic CO2 Trapping as carbamato ligand.” G Bresciani, M Bortoluzzi, F Marchetti, G Pampaloni, ChemSusChem, 2018, 11, 2737-2743.

“Synthesis of New Coordination Complexes of MF5 (M = Nb, Ta), and Insights into the Ta(V) Reduction” G Bresciani, T Funaioli, S Zacchini, M Hayatifar, F Marchetti, G Pampaloni, Inorganica Chimica Acta, 2018, 482, 498-502.

Oral communications at congress:

“Group 4 and Group 5 halocarbamates: synthesis, characterization and reactivity”. G. Bresciani, C. Forte, F. Marchetti, G. Pampaloni, S. Zacchini, XIII PhD-Chem Day, CIRCC meeting, Bologna (Italy), 10-11 March 2016

“Conversion of CO2 into Useful Chemicals Mediated by Early Transition Metal Complexes”. G.Bresciani, F. Marchetti, G. Pampaloni, CO2 RUCADI Meeting, Bari (Italy), 30-31 March 2017.

“Formation of Cyclic Carbonates via Dynamic CO2 Activation at Ambient Conditions using Iron(III) N,N-Dialkylcarbamates” G. Bresciani, M. Bortoluzzi, F. Marchetti, G. Pampaloni, XLVI Congresso Nazionale di Chimica Inorganica, Bologna (Italy), 10-13 September 2018.

Poster communications at congress:

“Synthesis and Characterization of New Carbamates of Early Transition Metals in High Oxidation State”. G.Bresciani, F. Marchetti, G. Pampaloni, S. Zacchini, XII Co.G.I.C.O. 2016, Genova (Italy).

“Conversion of CO2 into Cyclic Propylene Carbonate Catalyzed by Carbamato Metal Complexes”. G. Bresciani, F. Marchetti, G. Pampaloni, S. Zacchini, XI International School of Organometallic Chemistry, ISOC 2017, San Benedetto del Tronto (Italy).

“Synthesis of Cyclic Organic Carbonates From CO2 and Epoxides at Ambient Conditions Using Iron N,N-Dialkylcarbamates”. G. Bresciani, F. Marchetti, G. Pampaloni, Dalton 2018, Warwick (UK).