Synthesis and structure of 2,4,6-tribromophenoxytetraphenylbismuth

Abstract

Four new complexes of pentavalent bismuth are synthesized: Ph 3 Bi [ OC 6 H 2 ( Br 3 -2,4,6)] 2 , Ph 3 Bi [ OC 6 H 2 ( Cl 3 -2,4,6)] 2 , Ph 4 BiOC 6 H 2 ( Br 3 -2,4,6), and Ph 4 BiOC 6 H 2 ( Cl 3 -2,4,6) . Tetraphenylbismuth aroxides are produced by the disproportionation reaction of ligands from pentaphenylbismuth and triphenylbismuth diaroxides in toluene or from pentaphenylbismuth and phenol. Triphenylbismuth diaroxides are synthesized from phenol, triphenylbismuth, and hydrogen peroxide taken at a molar ratio of 2 : 1 : 1, respectively, in diethyl ether. According to the X-ray diffraction data, the bismuth atom surrounding in 2,4,6-tribromophenoxytetraphenylbismuth has the configuration of a trigonal bipyramid with the aroxyl ligand in the axial position. The Bi-C and Bi-O bond lengths are 2,184, 2.190, 2.234, and 2.514 Å, respectively, and the equatorial CSbC angles are equal to 111.4°, 121.3°, and 121.3° .

Formation of Bismuth(V) Thiolates: Protolysis and Oxidation of Triphenylbismuth(III) with Heterocyclic Thiols

“…Thus, bismuth(III) thiolates are common stable species and have a special relevance in biology and medicine 17. While both Hoppe and Whitmire8d and Sharutin et al 8a–c. have had some success in synthesizing triarylbismuth(V) phenoxides, there is no corresponding thiolate chemistry.…”

Synthesis, structure and properties of trivalent and pentavalent tricarbabismatranes

“…5 The bismatrane structure forced the cis arrangement of the two F atoms (F–Bi–F angle, 74.11(10)°), such an arrangement was observed for the first time in the monomeric triorganobismuth dihalides. 19–21 Bi–F bond lengths (average 2.109(2) Å) are comparable to those of terminal Bi–F bonds in other triorganobismuth difluorides (2.09–2.28 Å). 19…”

“…Since the pentavalent bismuth dichloride 7a is thermally stable, higher ring strain caused by the additional ring formation in the bismatrane and/or forced cis -arrangement of the two Cl atoms facilitated the reductive elimination. All triorganobismuth dihalides so far reported have two halogen atoms in trans orientation, 19–21 except one example that forms a dimer in the crystal through additional intermolecular Bi···F interactions. 19 e…”

Synthesis, Structure and Application of Aryl Bismuth Compounds

“…Показано, что трифенилвисмут окисляется пероксидом водорода в присутствии фенолов, содержащих преимущественно электроноакцепторные заместители, до соответствующих диароксидов трифенилвисмута (эфир, 20 С, 18 ч) (схема 19) [43,[53][54][55]. Изменение соотношения исходных реагентов в реакциях окислительного присоединения с участием фенолов или органосульфоновых кислот (1:1:1 вместо 1:1:2 мольн.…”