Silyl-Substituted Thioether Ligands and Their Ag(I) Complexes
作者:Chinwon Rim、Hongming Zhang、David Y. Son
DOI:10.1021/ic801580t
日期:2008.12.15
Silyl-substituted thioether ligands were prepared that differed in the identity and number of ligating groups attached to silicon and the nature of the alkyl groups on silicon. The ligand syntheses involved deprotonation of a thioether with n-butyllithium followed by reaction with the appropriate chlorosilane. Yields were 45-75% after purification. The majority of the ligands reacted with silver(I) triflate to give stable crystalline products in high yields that could be characterized by single-crystal X-ray crystallography. Depending on the ligand, the structures of the products ranged from discrete complexes to infinite polymeric structures. Apparent argentophilic interactions were commonly observed in the solid-state structures of the complexes (Ag-Ag = 2.909-3.196 angstrom).
Bis[bis(methylthio)lithiomethyl]dimethylsilanes: A useful reagent for the synthesis of polysilacarbacycles via disilylation
Bis[bis(methylthio)lithiomethyl]dimethylsilane was generated from bis[bis(methylthio)methyl]dimethylsilane by deprotonation with t-BuLi in THF and allowed to react with various dichloro(poly)silanes to give the corresponding 4- to 7-membered polysilacarbacycles in moderate to good yields. The methylthio groups in the cyclized products were readily removed by radical reduction with Bu3SnH.