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Unimolecular decomposition of H3CONO+*

✍ Scribed by Eldon E. Ferguson

Publisher
Elsevier Science
Year
1987
Tongue
English
Weight
447 KB
Volume
138
Category
Article
ISSN
0009-2614

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✦ Synopsis

A model for the decomposition of methylnitrite ions to produce protonated formaldehyde is proposed which invokes quantummechanical tunneling of hydrogen between the initial C and final 0 atoms. A barrier is adopted, guided by theoretical transitionstate calculations for H transfer from C to H in the methanol ion, which gives the low rate constant observed, a very small energy dependence for the decompositton rate constant and a very large isotope effect, z IO3 for H,CONO+ relative to DsCONO+. The D,CONO+ experiments are reinterpreted in the light of the present model. Internal mconsistencies in the previous interpretation suggest that the 34+ ion observed in D#ZONO+ decomposition may be D2NO' rather than D,COD'.

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