US EPA

1947521 

Journal Article 

Ionic fluorination of carbon monoxide as a route to gas-phase carbonylation of inert C-H and N-H bonds 

Grandinetti, F; Pepi, F; Ricci, A 

1996 

Yes 

Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765 

2 

5 

495-501 

English 

29178229 

10.1002/chem.19960020507 

WOS:A1996UP33900004 

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 NF3 and of NF2+ with CO. Combining the latter F+ transfer with the independently observed fluoride-ion abstraction by FCO+ from NF3 results in a catalytic cycle in which gaseous NF2+ ions promote the conversion of carbon monoxide into carbonic difluoride, F2CO, with nitrogen trifluoride as the source of F. 

carbon monoxide; carbonylations; fluorine compounds; gas-phase chemistry