From {Bi₂₂O₂₆} to Chiral Ligand‐Protected {Bi₃₈O₄₅}‐Based Bismuth Oxido Clusters

Abstract

The reaction of [Bi(22)O(26)(OSiMe(2)tBu)(14)] (1) in THF with salicylic acid gave [Bi(22)O(24)(HSal)(14)] (2) first, which was converted into [Bi(38)O(45)(HSal)(22)(OH)(2)(DMSO)(16.5)]·DMSO·H(2)O (3·DMSO·H(2)O) after dissolution and crystallization from DMSO. Single-crystal X-ray diffraction analysis and ESI mass spectrometry associated with infrared multi-photon dissociation (IRMPD) tandem MS experiments confirm the formation of the large and quite stable bismuth oxido cluster 3. The reaction of compound 2 with the butoxycarbonyl(BOC)-protected amino acids phenylalanine and valine (BOC-PheOH and BOC-ValOH), respectively, resulted in the formation of chiral [Bi(38)O(45)(BOC-AA)(22)(OH)(2)] (AA=deprotonated amino acid), as shown by a combination of different analytical techniques such as elemental analysis, dynamic light scattering, circular dichroism spectroscopy, and ESI mass spectrometry.

Homo‐ and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates

“…However, defined intermediates formed during the hydrolysis process of 3 , as reported for Ph 2 Bi(O 3 SR) (R=phenyl, 4‐tolyl), which decompose to BiO(O 3 SR) over ten years and as reported in our previous studies on bismuth silanolates, carboxylates, and nitrates, were not observed. Therefore, [Bi 6 O 4 (OH) 4 (NO 3 ) 6 ]⋅H 2 O ( A ; approach A) and [Bi 38 O 45 (OMc) 24 (dmso) 9 (H 2 O) 2 ]⋅2 DMSO⋅5 H 2 O ( B ; approach B) were used as preorganized starting materials and were treated with 6 and 24 equivalents of vinylsulfonic acid in DMSO, respectively (Scheme ).…”

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

“…Among the nuclearities observed for that ligand alone are [ Oxidoclusters supported by alkoxides, other carboxylates and hexafluoroacetylacetonate have also been reported. 7,30,31,[33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] They contain a core composed of Bi(III) and oxygen atoms that has an overall positive charge. These cores are then surrounded by negatively charged carboxylate ligands to form an overall neutral compound.…”

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)

“…The chemistry of these oxo clusters has been reviewed. 9,[11][12][13][14][15][16][17] Often when reacting bismuth halides with sodium salts of alkoxides or carboxylates, oxo-compounds are obtained. 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.…”