Rearrangements in metastable ion decompositions of protonated propylamines

✍ Scribed by Henri E. Audier; Thomas Hellman Morton

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: English
• Weight: 715 KB
• Volume: 28
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210281037

✦ Synopsis

Decomposition of nPrNH,+ to NH,+ does not occur via vicinal elimination. Hydrogen transfer takes place from all positions of the alkyl chain. Intermediacy of either an ion-neutral complex, (iPr+ NH,], or rearrangement to iPrNH,+ is required. SCF calculations were used to probe the potential energy surface. There is a minimum corresponding to [iPr+ NH,I, in which the nitrogen lone pair points towards the machine hydrogen and is 2.1 A away from it, and another, less stable, minimum corresponding to a hydrogen-bonded structure, H,N--.H,CCHCH,+, in which one methyl hydrogen is 2.0 A from the nitrogen. Density of states estimates suggest that a vibrationally excited complex can live for the order of 100 ps before either collapsing to iPrNH,' or yielding NH,' and propene.