Abstract
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 with the general formula [HPS3BiX4]2. On the basis of their solid-state structures determined by single-crystal X-ray diffraction, these compounds exhibit discrete bis-zwitterionic assemblies consisting of two phosphonium units [HPS3]+ linked to a central dibismuthate core [Bi2X8]2– via S→Bi dative interactions. Remarkably, the phosphorus center of the PS3 ligand undergoes protonation with hydrochloric acid. This is in stark contrast to the protonation of phosphines commonly observed with hydrogen halides resulting in equilibrium. To understand the important factors in this protonation reaction, 31P NMR experiments and DFT computations have been performed. Furthermore, the dibismuthate linker was utilized to obtain the coordination polymer {[AgPS3BiCl3(OTf)]2(CH3CN)2}∞, in which dicationic [Ag(PS3)]22+ macrocycles containing five-coordinate silver centers connect the dianionic [Bi2Cl6(OTf)2]2– dibismuthate fragments. The bonding situation in these dibismuthates has been investigated by single-crystal X-ray diffraction and DFT calculations (NBO analysis, AIM analysis, charge distribution).
Highlights
IntroductionDissolving bismuth trichloride in hydrochloric acid leads to the formation of the [BiCl4]− monoanion and the [BiCl5]2− dianion.[1,2] Following these simple anions, a plethora of more complex oligomeric and polymeric halobismuthate anions of have been discovered.[3−5] the general formula [BinXm]3n−m Due to the weakness of the bismuth−halogen bond, these complexes can undergo various association and dissociation processes in solution; in the solid state, the versatility of coordination modes around the bismuth center results in a high structural diversity
Halobismuthate(III) anions have been known for over 100 years
Organic hybrid material was analyzed by multinuclear NMR spectroscopy, and the 31P{1H} NMR spectrum in CD2Cl2 exclusively shows a singlet resonance at −20.8 ppm, which is significantly different from that of PS3BiCl3 (−37.0 ppm in C6D656) or the free ligand PS3 (−36.9 ppm in C6D6,56 −36.2 ppm in CD2Cl2), indicating a change in the chemical environment of the phosphorus center
Summary
Dissolving bismuth trichloride in hydrochloric acid leads to the formation of the [BiCl4]− monoanion and the [BiCl5]2− dianion.[1,2] Following these simple anions, a plethora of more complex oligomeric and polymeric halobismuthate anions of have been discovered.[3−5] the general formula [BinXm]3n−m Due to the weakness of the bismuth−halogen bond, these complexes can undergo various association and dissociation processes in solution; in the solid state, the versatility of coordination modes around the bismuth center results in a high structural diversity. [Bi2Xm]6−m, where m can the rarest species known are for [Bi2X8]2−, whose centrosymmetric geometry exhibits two edge-sharing square pyramids and a stereochemically active lone pair at each of the bismuth centers (see Figure 1).[19−22] In contrast, in the other three anions
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