Towards a molecular model for bismuth(iii) subsalicylate. Synthesis and solid-state structure of [Bi(Hsal)3(bipy)(C7H8]2 and [Bi(Hsal)(sal)(1,10-phenanthroline)(C7H8]2

Abstract

The synthesis and characterization of the first bismuth salicylate complexes, stabilized by chelating amine ligands, offers the possibility for detailed investigation of molecular precursors of the biologically significant compound bismuth subsalicylate (BSS).

Towards a Structural Understanding of the Anti‐Ulcer and Anti‐Gastritis Drug Bismuth Subsalicylate

“…The bonding to the outlying Bi III centers corresponds to highly complex bridging modes (see below) with no evidence of any interactions with the ortho hydroxy oxygen atoms. This is similar to the bonding in [Bi(Hsal) 3 -(bpy)] 2 ·(C 7 H 8 ) 2 and in contrast to that in [Bi(Hsal)(sal)-(phen)] 2 ·(C 7 H 8 ) 2 [19] (phen = 1, 10-phenanthroline). If one considers all Bi À O bond lengths in the structures up to 3.1 , three broad categories become evident: very short bonds (shortest 2.06 in 1 and 2.09 in 2) primarily found in the oxide core, and medium and long bonds resulting from asymmetric coordination of the carboxylate ligands.…”

“…As a first step there have been attempts to model the structures of BSS (and CBS) through the formation and structural elucidation of a variety of bismuth carboxylates. [2,17,18] The most important of these are tris-substituted bismuth salicylate [Bi(Hsal) 3 ] (H 2 sal = (2-HO)C 6 H 4 COOH) "trapped" by chelating amines, for example, [Bi(Hsal) 3 -(bpy)] 2 ·(C 7 H 8 ) 2 , (bpy = 2,2'-bipyridine), [19] bismuth thiosalicylate complexes, [20] and the structurally uncharacterized [Bi(Hsal) 3 ] compound. [21,22] These model compounds, however, do not address the "sub" part of subsalicylate which, as the name infers, requires partial hydrolysis of the BiL 3 species and concomitant hydroxide/oxide formation, resulting in the typical insolubility of these compounds.…”

Synthesis and structural studies of the simplest bismuth(iii) oxo-salicylate complex: [Bi4(μ3-O)2(HO-2-C6H4CO2)8]·2Solv (Solv = MeCN or MeNO2)

“…We discovered that protonolysis of BiPh 3 using acidic organic compounds can avoid the formation of oxo ligands and have applied this methodology to the production of [Bi(OC 6 F 5 ) 3 (toluene)] 2 , Bi(Hsal) 3 and various derivatives thereof. 8,18,19 This approach avoids the sodium halide salt metathesis byproducts, yielding only volatile benzene. Subsequent hydrolysis of these compounds by dissolution in wet solvents leads to a variety of bismuth-oxo alkoxides and carboxylates.…”

“…Consequently, we have explored the effect of solvent on the protonolysis of BiPh 3 in a variety of solvents. Herein we report the facile synthesis of the tetranuclear oxo cluster Bi 4 O 2 (Hsal) 8 , which is found to be solvated by two molecules of either MeCN and MeNO 2 in the solid state.…”

In Situ Preparation, Structure, Photoluminescence and Theoretical Study of an Unusual Bismuth Complex

“…To the best of my knowledge, this is the first bismuth compound with a methylated 2,2'-bipy moiety, although several bismuth compounds with a 2,2'-bipy moiety have been reported. [28][29][30][31] Bismuthate compounds are well-known for their interesting photoluminescent behaviors and they have been found applications in the fields of chemical sensors, electrochemical displays, light-emitting diodes (LEDs), photoluminescent materials, and so on. 32,33 Taking into account the good photoluminescent properties of bismuthate and 2,2'-bipy, in the present work, we investigate the photoluminescent behaviors of compound 1 with solid-state samples at room temperature.…”