Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers

摘要: Adducts of bismuth trihalides BiX3 (X = Cl, Br, I) and the PS3 ligand (PS3 P(C6H4-o-CH2SCH3)3) react with HCl to form inorganic/organic hybrids general formula [HPS3BiX4]2. On basis their solid-state structures determined by single-crystal X-ray diffraction, these compounds exhibit discrete bis-zwitterionic assemblies consisting two phosphonium units [HPS3]+ linked a central dibismuthate core [Bi2X8]2- via S→Bi dative interactions. Remarkably, phosphorus center undergoes protonation hydrochloric acid. This is in stark contrast phosphines commonly observed hydrogen halides resulting equilibrium. To understand important factors this reaction, 31P NMR experiments DFT computations have been performed. Furthermore, linker was utilized obtain coordination polymer {[AgPS3BiCl3(OTf)]2(CH3CN)2}∞, which dicationic [Ag(PS3)]22+ macrocycles containing five-coordinate silver centers connect dianionic [Bi2Cl6(OTf)2]2- fragments. The bonding situation dibismuthates has investigated diffraction calculations (NBO analysis, AIM charge distribution).