DFT theoretical studies of alkali metal acetylenic thiolates

It follows from DFT calculations of acetylenic thiolates and their structural isomers-thioketenes and thiirenes that only the acetylenic type is stable. Most of the negative charge is concentrated on the sulfur atom. The influence of the cation (Li, Na, K) and the acetylenic substituent on the electronic structure and geometry of the thiolates is investigated. DFT calculations of IR and C-13 NMR spectra of phenylethynethiolate potassium are in agreement with experimental data. (C) 2002 Elsevier Science Ltd. All rights reserved.