D-orbital effects and the structure of the alpha-thiocarbanion

✍ Scribed by Saul Wolfe; Lawrence A. LaJohn; Fernando Bernardi; Angelo Mangini; Glauco Tonachini

• Book ID: 104226600
• Publisher: Elsevier Science
• Year: 1983
• Tongue: French
• Weight: 294 KB
• Volume: 24
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)94536-2

✦ Synopsis

Improved computational results show that sulfur-3d orbital effects are essential for the nroner descrintion of the bonding in the aloha-thiocarbanions -CHzSH and -CH2SCHs. The nature of I . the d-orbital effects has been analyzed, and reasons for the earlier failures to find these effects have been determined. Sulfur-containing carbanions -CH2-Sabc contain a number of interrelated geometrical parameters. Because, in particular, the C-S bond lengths, C-S torsional angles and carbon valence angles of such species are strongly coupled,] theoretically derived geometries can be greatly in error when any one of these parameters is not optimized properly. As was found recently in a comprehensive reexamination of sulfonium .:nd phosphonium ylides, such errors naturally bias attempts to interpret the resulting structures or to analyze the resulting wavefunctions, in ways that would not have been anticipated.