Thiophile Reaktionen an Thiocarbonylverbindungen und deren Redoxverhalten

Abstract

The review describes thiophilic reactions of thiocarbonyl compounds with C‐ and S‐nucleophiles. They occur more frequently than has been supposed up to now, especially between vicinal thiocarbonyl systems and S‐nucleophiles. A general relation between thiophilic reactions and the redox behaviour of the system and a possibility to estimate approximately the thiophilic properties are discussed. Some conclusions for the synthesis and the behaviour of thiocarbonyl compounds are drawn.

Synthesis of Bicyclic P,S-Heterocycles via the Addition of Thioketones to a Phosphorus-Centered Open-Shell Singlet Biradical

“…Another important consequence is the smaller highest occupied molecular orbital–lowest unoccupied molecular orbital gap in the CS group compared to the CO group . Furthermore, a decrease in the difference of the π charge densities at the carbon and sulfur can be observed, and one finds lowered ionization potentials as well as a red shift of the n → π* and π → π* transitions in the UV–vis spectrum …”

“…26 Furthermore, a decrease in the difference of the π charge densities at the carbon and sulfur can be observed, and one finds lowered ionization potentials as well as a red shift of the n → π* and π → π* transitions in the UV−vis spectrum. 27 Both alkyl-and aryl-substituted thioketones are known. Some of the first examples of isolated stable thioketones are shown in Scheme 2.…”