engleski

Alkane- and arene-oxodiazonium ions: experimental results leading to an ab initio theoretical investigation

Alkaneoxodiazonium ions, which are closely analogous to alkanediazonium ions, have been detected as reactive intermediates in acid-catalysed reactions of nitrosohydroxylamines and deamination-type reactions. The isomers have been compared by high level MO investigations of the reactions of nitrous oxide with cationic electrophiles such as H+, CH3+, Me3C+, and PhCH2+. Strongly bonded species are formed in reactions with the powerfully electrophilic H+ and CH3+, and the resulting isomeric pairs differ considerably in stabilities ; less stable species are formed with Me3C+ and PhCH2+ and the isomeric complexes so formed have similar stabilities. Two isomers of PhN2O+, analogous to phenyldiazonium ion, PhN2+, are calculated to be stable ions with the end-N-bonded isomer being preferred over the O-bonded ion at MP4 and G3 levels of theory. Both are non-planar with the phenyl ring at 90 o to the non-linear N2O residue. Syntheses of salts of ArN2O+ are now planned.

ab initio calculations; dediazoniation; diazonium ion; deamination; oxodiazonium ion; carbenium ion; carbocation

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