Premium
Ionic Fluorination of Carbon Monoxide as a Route to Gasphase Carbonylation of Inert CH and NH Bonds
Author(s) -
Grandinetti Felice,
Pepi Federico,
Ricci Andreina
Publication year - 1996
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19960020507
Subject(s) - chemistry , carbon monoxide , fourier transform ion cyclotron resonance , dissociation (chemistry) , toluene , inorganic chemistry , benzene , ionic bonding , mass spectrometry , difluoride , photochemistry , carbonylation , catalysis , ion , carbonyl sulfide , sulfur , organic chemistry , chromatography
Gaseous FCO + ions from the ionization of mixtures of nitrogen trifluoride and carbon monoxide execute selective and efficient CO‐functionalization of the C–H bonds of benzene and toluene and of the N–H bond of ammonia. The occurrence of these carbonylation reactions has been unambiguously ascertained by Fourier‐transform ion cyclotron resonance (FT‐ICR) spectrometry, and the details of the structure and the mechanism of formation of the precursor FCO + ions have been investigated. FT‐ICR experiments show that these ions, structurally assigned as F–C–O + by collisionally activated dissociation (CAD) spectrometry, arise from the reaction of CO .+ with NF 3 and of NF + 2 with CO. Combining the latter F + transfer with the independently observed fluoride‐ion abstraction by FCO + from NF 3 results in a catalytic cycle in which gaseous NF + 2 ions promote the conversion of carbon monoxide into carbonic difluoride, F 2 CO, with nitrogen trifluoride as the source of F.