Exploration of solvent free and/or microwave assisted syntheses of bismuth(iii) thiolates

A dinuclear Bi(III) complex of a 1,3-disubstituted imidazole-2-thione and its use as a transmetallation agent toward Pd(II)

“…Understanding the metalloselectivity with which a ligand or a substrate interacts with a heterometallic system are thus of considerable relevance. Coordination complexes of Bi(III) with imidazole-based thioureas have been reported in the form of mononuclear complexes of N-(mono)substituted imidazole-2-thiones [4][5][6][7], mono-and dinuclear complexes of 1,3-disubstituted imidazole-2-thiones (imt) [8][9][10][11][12], and complexes of benzimidazole-2-thiones [4,13,14] as well as complexes of imidazole-2-thiones fused with other heterocycles [15]. Bi(III) complexes containing polydentate imidazole-2-thione derivatives include chelating bis(imidazole-2-thiones) [13,16] and complexes of tripodal scorpionate tris(imidazole-2-thione) hydroborates [17][18][19][20] (see Scheme 1 for an outline of most common ligand types).…”

Microwave-Assisted Synthesis of Coordination and Organometallic Compounds

“…(Mondal et al, 2009). BiPh 3 was treated with thiols of varying pKa and functionality (2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptopyrimidine, 2-mercapto-1-methylimidazole and 2-mercaptobenzoic acid) in a 1:3 ratio under a variety of reaction conditions: with toluene or mesitylene under standard reflux conditions and under microwave irradiation, and solvent free with conventional and microwave heating (Andrews et al, 2007). As a result, several reactions yielded the trissubstitution product in good yield and high purity; 2-mercaptobenzoic acid gave the complex Bi 2 L 3 in all reactions carried out in solvent and PhBiL when solvent free, both complexes containing the doubly deprotonated dianion (L = -O 2 C-C 6 H 4 -S-).…”

Mechanosynthesis of the Metallodrug Bismuth Subsalicylate from Bi2O3 and Structure of Bismuth Salicylate without Auxiliary Organic Ligands

“…[2] Mechanochemistry can be very efficient for the synthesis of metal-organic frameworks (MOFs) [3] and magnesium-based pharmaceuticals [4] directly from inexpensive and otherwise inert materials, such as metal oxides or carbonates. [7][8][9][10][11][12] At least three [5] We now demonstrate how ion-and liquid-assisted grinding (ILAG), previously utilized for the mechanosynthesis of large-pore MOFs and zeolitic imidazolate frameworks [5,6] based on zinc, can be extended to the pharmaceutical chemistry of bismuth oxide.…”

“…These are the API bismuth subsalicylate BiO(Hsal), the disalicylate (2) with assigned formula Bi 2 O(Hsal) 4 , [8] and the trisalicylate (3) involving bismuth and salicylic acid in the 1:3 stoichiometric ratio. [10] The potential of mechanochemistry to generate bismuth carboxylates was revealed by Andrews and co-workers, [11,12] who investigated combined mechano-and thermochemical routes involving carboxylic acids and triphenylbismuth. Models for 1 and its biological activity were initially devised by Thurston et al [9] who used auxiliary chelating ligands to trap discrete oligonuclear clusters of Bi 3+ and salicylate anions (Hsal À ), and by Burford et al who explored complexation of Bi 3+ with thiosalicylic acid.…”

“…[7] The pharmaceutical value of bismuth complexes with salicylic acid (H 2 sal) has been established over a century ago and still remains an area of active research. [7][8][9][10][11][12] At least three different forms of bismuth salicylate, which differ in the stoichiometric ratio of bismuth and H 2 sal, have been reported. These are the API bismuth subsalicylate BiO(Hsal), the disalicylate (2) with assigned formula Bi 2 O(Hsal) 4 , [8] and the trisalicylate (3) involving bismuth and salicylic acid in the 1:3 stoichiometric ratio.…”