Diazenyl oxide anions, RN=NO−, are readily prepared in the gas phase by reaction of amide ions with neopentylnitrite. When subjected to collision-induced dissociation during injection into the second flow tube of a flowing afterglow selected ion flow tube (FA-SIFT), they form the same product ions observed previously from the reaction of strongly basic anions with N2O, including diazoanions, alkoxide ions and vinyl anions; thus supporting the postulate that the initial attack of these ions on N2O is at the terminal nitrogen atom. More importantly, this new procedure allows the synthesis of many new ions which could not be prepared directly from reactions with N2O.
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References
1.
For some leading references on the gas-phase reactions of anions with N2O see: (a) BierbaumV.M.DePuyC.H. and ShapiroR.H., J. Am. Chem. Soc.99, 5800 (1977); (b) KassS.R.FilleyJ.Van DorenJ.M. and DePuyC.H., J. Am. Chem. Soc.108, 2849 (1986).
2.
For some leading references which describe the use of simple triatomics such as N2O to distinguish isomeric anions in the gas phase see: (a) AndristA.H.DePuyC.H. and SquiresR.R., J. Am. Chem. Soc.106, 845 (1984); (b) FroelicherS.W.FreiserB.S. and SquiresR.R., J. Am. Chem. Soc.108, 2853 (1986).
3.
DahlkeG.D. and KassS.R., Int. J. Mass Spectrom. Ion Proc.117, 633 (1992).
4.
DawsonJ.H.J. and NibberingN.M.M., J. Am. Chem. Soc.100, 1928 (1978).
5.
BarlowS.E. and BierbaumV.M., J. Chem. Phys.92, 3442 (1990).
6.
DunkinD.B.FehsenfeldF.C. and FergusonE.E., J. Chem. Phys.53, 987 (1970).
7.
SheldonJ.C.O'HairR.A.J.DownardK.M.GronertS.KremppM.DePuyC.H. and BowieJ.H., Aust. J. Chem.48, 155 (1995).
8.
Van DorenJ.M.BarlowS. E.DePuyC.H. and BierbaumV.M., Int. J. Mass Spectrom. Ion Proc.81, 85 (1987).
9.
The gas-phase reactions of anions with alkyl nitrites have previously been described: (a) NoestA.J. and NibberingN.M.M., Adv. Mass Spectrom.8A, 227 (1979); (b) KingG.K.MaricqM.M.BierbaumV.M. and DePuyC.H., J. Am. Chem. Soc.103, 7133 (1981).
10.
GronertS.O'HairR.A.J.ProdnukS.SülzleD.DamrauerR. and DePuyC.H., J. Am. Chem. Soc.112, 997 (1990).
11.
BierbaumV.M.DePuyC.H.ShapiroR.H. and StewartJ.H., J. Am. Chem. Soc.98, 4229 (1976).
12.
McGarveyJ.J. and McGrathW.B., Trans. Faraday Soc.60, 2196 (1964).
13.
Gas-phase acidities and other thermochemistry are taken from: NIST Standard Reference Database 19B: NIST Negative Ion Energetics Database Version 2.07. Program written/data compilation by BartmessJohn E., Department of Chemistry, University of Tennessee, Knoxville, TN 37996–1600, USA. This compilation is based on original data from Gas-phase Ion and Neutral Thermochemistry, LiasS.G.BartmessJ.E.LiebmanJ.F.HolmesJ.L.LevinR.D. and MallardW.G., J. Phys. Chem. Ref. Data17, Suppl. 1 (1988).
14.
SuT. and BowersM.T., Int. J. Mass Spectrom. Ion Phys.12, 347 (1973).
15.
The related Smiles rearrangement readily occurs in the gas phase in the absence of activating groups: EichingerP.C.H.BowieJ.H. and HayesR.N., J. Am. Chem. Soc.111, 4224 (1989).
16.
For another alternative synthesis of vinyl anions see: AndersonK.K. and KassS.R., Tetrahedron Lett.30, 3045 (1989).
