Dialkynyl selenides: Synthesis, 13C NMR spectra, and molecular orbital calculations

✍ Scribed by Toshiaki Murai; Atsushi Shimizu; Shūji Tatematsu; Kazuhiko Ōno; Takahiro Kanda; Shinzi Kato

• Book ID: 102228836
• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 351 KB
• Volume: 5
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520050107

✦ Synopsis

Reactions of SeCl, with lithium bidtrimethyl-sily1)amide and terminal acetylenes in the presence o f BuLi or AIBN affiwded the corresponding dialkynyl selenides in moderate to high yields. The reaction may proceed via a selenium amide 7 and an alkynyl selenium amide 8. The comparison ofI3C NMR spectra of dialkynyl selenides and tellurides has disclosed that the differences of the chemical shift of acetylenic carbons between Se and Te derivatives are consistent regardless of their substitution patterns. Ab initio molecular orbital calculations are reported for dialkynyl ether and chalcogenides. The calculated structures, charge distributions, and orbital energies are discussed.

Dialkynyl ether:; and chalcogenides are compounds of great interest because of their potential synthetic utility as well as their structural properties, resulting from the situation that two electronically rich alkynyl groups are attached to an electronegative i5tom [ 11. However, only limited examples have been reported concerning synthetic efforts to attain :such compounds. Several kinds of dialkynyl sulfides have been prepared by monoor