Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Computational and Spectroscopic Studies on the Formation of Halogen-Bonded Complexes Between Tertiary Amines and CBr4 and Application in the Light-Mediated Amino Acid Coupling
Δημιουργός/Συγγραφέας:	Routsi, E Alexandros Mantzourani, Christiana Rrapi, Marie Mountanea, Olga G Kokotou, Maroula G [EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter Kokotos, Christoforos G Kokotos, George
Ημερομηνία:	2024-09
Γλώσσα:	Αγγλικά
ISSN:	2192-6506 2192-6506
DOI:	10.1002/cplu.202400019
Άλλο:	38712501
Περίληψη:	In recent years, halogen-bonded complexes (XBCs), in solution, have played a pivotal role in inducing photochemical organic reactions. In this work, we explore the ability of various tertiary amines to act as XB acceptors in the presence of the XB donor CBr4 by computational and spectroscopic studies. DFT studies clearly showcase the formation of XBCs between the studied tertiary amines and CBr4. Simultaneously, computational and experimental UV-Vis studies display intense red shifts that are consistent with charge transfer observed from tertiary amines to CBr4. A detailed NMR study revealed a clear chemical shift of the carbon carrying the bromine atoms upon mixing the XB acceptor with the donor, suggesting that this spectroscopic technique is indeed an experimental tool to identify the generation of XBCs. An application of the ability of such XBCs to activate a carboxylic acid under UVA irradiation or sunlight is presented for amino acid coupling. Among the various tertiary amines studied, the pair DABCO-CBr4 was found to work well for the photochemical amide bond formation. Direct infusion-HRMS studies allowed us to propose a general mechanism for the photochemical amino acid coupling in the presence of a tertiary amine and CBr4, initiated by the photoactivation of an XBC.
Τίτλος πηγής δημοσίευσης:	ChemPlusChem
Τόμος/Κεφάλαιο:	89
Τεύχος:	9
Θεματική Κατηγορία:	[EL] Φωτοχημεία[EN] Photochemistry [EL] Οργανική χημεία[EN] Organic chemistry
Λέξεις-Κλειδιά:	DFT calculations DI-HRMS studies NMR studies amide bond formation halogen bonding
EU Grant:	1st Call for H.F.R.I. Research Projects to support FacultyMembers & Researchers and the Procurement of High-costresearch equipment grant H.F.R.I. PhD Fellow-ship 5th Call for PhD Fellowships
EU Grant identifier:	655 1338 19213
Κάτοχος πνευματικών δικαιωμάτων:	© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH
Όροι και προϋποθέσεις δικαιωμάτων:	This is an open access article under the terms of the Creative Commons Attribution-Non Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
Ηλεκτρονική διεύθυνση στον εκδότη (link):	https://doi.org/10.1002/cplu.202400019
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο