Enhancement of the σ-hole on the halogen atom of aryl halides due to perfluorination of the ring is demonstrated by use of the Extended Townes-Dailey (ETD) model coupled to a Natural Atomic Orbital Bond analysis on two perfluorinated aryl halides (C6F5Cl and C6F5Br) and their hydrogenated counterparts. The ETD analysis, which quantifies the halogen p-orbitals populations, relies on the nuclear quadrupole coupling constants which in this work are accurately determined experimentally from the rotational spectra. The rotational spectra investigated by Fourier-Transform microwave spectroscopy performed in supersonic expansion are reported for the parent species of C6F5Cl and C6F5Br and their 13C, 37Cl or 81Br substituted isotopologues observed in natural abundance. The experimentally determined rotational constants combined with theoretical data at the MP2/aug-cc-pVTZ level provide precise structural information from which an elongation of the ring along its symmetry axis due to perfluorination is proved.
σ-Hole activation and structural changes upon perfluorination of aryl halides: Direct evidence from gas phase rotational spectroscopy / Lv D.; Maris A.; Evangelisti L.; Maggio A.; Song W.; Elliott A.A.; Peebles S.A.; Neill J.L.; Muckle M.T.; Pate B.H.; Peebles R.A.; Melandri S.. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - STAMPA. - 23:33(2021), pp. 18093-18101. [10.1039/d1cp03023j]
σ-Hole activation and structural changes upon perfluorination of aryl halides: Direct evidence from gas phase rotational spectroscopy
Lv D.Primo
Investigation
;Maris A.Secondo
Methodology
;Evangelisti L.Formal Analysis
;Song W.Investigation
;Melandri S.
Ultimo
Writing – Original Draft Preparation
2021
Abstract
Enhancement of the σ-hole on the halogen atom of aryl halides due to perfluorination of the ring is demonstrated by use of the Extended Townes-Dailey (ETD) model coupled to a Natural Atomic Orbital Bond analysis on two perfluorinated aryl halides (C6F5Cl and C6F5Br) and their hydrogenated counterparts. The ETD analysis, which quantifies the halogen p-orbitals populations, relies on the nuclear quadrupole coupling constants which in this work are accurately determined experimentally from the rotational spectra. The rotational spectra investigated by Fourier-Transform microwave spectroscopy performed in supersonic expansion are reported for the parent species of C6F5Cl and C6F5Br and their 13C, 37Cl or 81Br substituted isotopologues observed in natural abundance. The experimentally determined rotational constants combined with theoretical data at the MP2/aug-cc-pVTZ level provide precise structural information from which an elongation of the ring along its symmetry axis due to perfluorination is proved.File | Dimensione | Formato | |
---|---|---|---|
PCCP_peebles_cut.pdf
Open Access dal 11/02/2024
Tipo:
Postprint
Licenza:
Licenza per Accesso Aperto. Creative Commons Attribuzione - Non commerciale - Non opere derivate (CCBYNCND)
Dimensione
1.72 MB
Formato
Adobe PDF
|
1.72 MB | Adobe PDF | Visualizza/Apri |
C6F5X-PCCP-ESI.docx
accesso aperto
Tipo:
File Supplementare
Licenza:
Licenza per Accesso Aperto. Creative Commons Universal Donazione al Pubblico Dominio (CC0 1.0)
Dimensione
270.41 kB
Formato
Microsoft Word XML
|
270.41 kB | Microsoft Word XML | Visualizza/Apri |
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.