A molecular orbital study of alkoxy allyl and vinyl anions

✍ Scribed by Angelo R. Rossi; Brian D. Remillard; Steven J. Gould

• Publisher: Elsevier Science
• Year: 1978
• Tongue: French
• Weight: 275 KB
• Volume: 19
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)95223-2

✦ Synopsis

An adequate description of the electronic structure of anions poses an important challenge for the computational chemist.' The purpose of the present work is to explain how substituted vinyl anions (l,X=OR) can be stabilized relative to the isoelectronic substituted ally1 anions @,X=OR). Recent experimental results on substituted alkoxyalkenesL produced methylation exclusively at the a-vinyl position rather than yielding an allyl-alkylated product. On the other hand, calculations on unsubstituted propenyl and ally1 anions (&X=H) have shown that the ally1 anion is significantly more stable than the propenyl anion for a variety of geometrical distortions. 3

In this work it will be shown how this trend can be modified by the substitution of an alkyoxy group for a hydrogen. The approach that we have followed in describing differences in stability and reactivity is the use of qualitative molecular orbital bonding concepts buttressed by symnetry arguments4 as well as quantitative calculations on selected anions. 5