RT info:eu-repo/semantics/article
T1 How aromatic fluorination exchanges the interaction role of pyridine with carbonyl compounds: The formaldehyde adduct
A1 López Alonso, Juan Carlos
A1 Macario Farto, Alberto
A1 Maris, Assimo
A1 Alkorta, Ibon
A1 Blanco Rodríguez, Susana
K1 Aromatic fluorination
K1 Pyridine
K1 Carbonyl compounds
K1 Pentafluoropyridine
K1 Formaldehyde
K1 23 Química
AB The rotational spectrum of the weakly bound complexpentafluoropyridineꞏꞏꞏformaldehyde has been investigated usingFourier transform microwave spectroscopy. From the analysis of therotational parameters of the parent species and of the 13C and 15Nisotopologues, the structural arrangement of the adduct has beenunambiguously established. The full ring fluorination of pyridine has adramatic effect on its binding properties: It alters the electron densitydistribution at the π-cloud of pyridine creating a π-hole and changingits electron donor-acceptor capabilities. In the complex, formaldehydelies above the aromatic ring with one of the oxygen lone pairs, asconventionally envisaged, pointing toward its centre. This lonepairꞏꞏꞏπ-hole interaction, reinforced by a weak C-HꞏꞏꞏN interaction,indicates an exchange of the electron-acceptor roles of bothmolecules when compared to the pyridineꞏꞏꞏformaldehyde adduct.Tunnelling doublets due to the internal rotation of formaldehyde havealso been observed and analysed leading to a discussion on thecompetition between lone pairꞏꞏꞏπ-hole and π ꞏꞏꞏπ staking interactions.
PB Wiley
SN 0947-6539
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/48998
UL https://uvadoc.uva.es/handle/10324/48998
LA eng
NO Chemistry – A European Journal, 2021, vol.  27, n. 55,  p.13870 –13878
NO Producción Científica
DS UVaDOC
RD 26-abr-2024