Gas-phase nitrosation of ethylene and related events in the C2H4NO+ landscape.
The C2H4NO(+) system has been examined by means of quantum chemical calculations using the G2 and G3B3 approaches and tandem mass spectrometry experiments. Theoretical investigation of the C2H4NO(+) potential-energy surface includes 19 stable C2H4NO(+) structures and a large set of their possible interconnections. These computations provide insights for the understanding of the (i) addition of the nitrosonium cation NO(+) to the ethylene molecule, (ii) skeletal rearrangements evidenced in previous experimental studies on comparable systems, and (iii) experimental identification of new C2H4NO(+) structures. It is predicted from computation that gas-phase nitrosation of ethylene may produce C2H4(*)NO(+) adducts, the most stable structure of which is a pi-complex, 1, stabilized by ca. 65 kJ/mol with respect to its separated components. This complex was produced in the gas phase by a transnitrosation process involving as reactant a complex between water and NO(+) (H2O.NO(+)) and the ethylene molecule and fully characterized by collisional experiments. Among the other C 2H 4NO (+) structures predicted by theory to be protected against dissociation or isomerization by significant energy barriers, five were also experimentally identified. These finding include structures CH3CHNO(+) (5), CH 3CNOH (+) ( 8), CH3NHCO(+) (18), CH3NCOH(+) (19), and an ion/neutral complex CH2O...HCNH(+) (12).
Gerbaux
Pascal
P
Laboratoire de Chimie Organique, Université de Mons-Hainaut, Avenue Maistriau 19, B-7000 Mons, Belgique.
Dechamps
Noemie
N
Flammang
Robert
R
Nam
Pham Cam
PC
Nguyen
Minh Tho
MT
Djazi
Fayçal
F
Berruyer
Florence
F
Bouchoux
Guy
G
D005030:Ethylenes / Q000737:chemistry*; D005740:Gases / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009569:Nitric Oxide / Q000737:chemistry*; D015538:Nitrosation; D013237:Stereoisomerism; D013499:Surface Properties
D005030:Ethylenes; D005740:Gases; D009569:Nitric Oxide; C036216:ethylene