The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(iii) ions

Abstract

Alkali metal salts of a novel Janus scorpionate ligand [(Tr(Me))](-) with hard and soft donor sites (N, S) were synthesized by the reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with NaBH4 and KBH4, respectively, via Trofimenko's protocol. The resulting compounds were the sodium and potassium complexes [Na(Tr(Me))] (1), [K(Tr(Me))] (2) and the mixed ion compound [KNa(Tr(Me))] (3). [K(Tr(Me))] (2) was reacted with bismuth(III) chloride to afford the complexes [Bi(Tr(Me))(Cl)(μ-Cl)2]2 (5) and [Bi(Tr(Me))(Cl)2(μ-Cl)]n (6). Compound 5 was formed when 2 was applied to BiCl3 in a molar ratio 2:1, while 6 was achieved when a ratio of 1:1 was used. The reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with BiCl3 led to the formation of the complex [Bi(L)4(Cl)2]Cl (7). The products were characterized by NMR and IR spectroscopy, elemental analyses and mass spectrometry. Solid state structures were determined by X-ray diffraction of single crystals of 1, 3, 3a, 5, 6 and 7. The alkali metal scorpionates 1-3 are coordination polymers with alternating orientation of the ligands. They dissociate in solution as observed in NMR measurements. Negative mode ESI-MS data also indicate the presence of monomers. The bismuth complex 5 is dimeric and 6 is polymeric, and both are bridged via chloro ligands. The three bismuth complexes 5, 6 and 7 have highly distorted octahedral coordination geometries. The influence of the stereochemically active lone pair was found to be most pronounced in the dimeric complex 5. The ligand Tr(Me) and all bismuth complexes were also screened for their photo-luminescence activity. Whereas solutions of Tr(Me) exhibit no luminescence, 7 is only emissive at 77 K, and 5 is emissive both at r.t. and 77 K.

Synthesis and Characterization of Sterically Congested Mesityltris(imidazolium) Salts and the Corresponding Highly Crystalline Tris-selone Derivatives

“…[13,25] Imidazole selones, as pecial class of heteroketones, have gained increasing interest in recenty ears as efficient ligating agents in lieu of traditional N-heterocyclic carbenes. In fact, mono-and bis-imidazole selones have been extensively used to generate transitionmetal-based complexes [26][27][28][29][30][31][32][33][34][35][36][37][38] and have furtherb een employed in versatile catalytic applications, such as polymerization [39] and the reduction of nitrobenzenes. [40] Moreover,s uch selenoketones have been used as inhibitors of lactoperoxidase-catalyzed oxidation and tyrosine nitration, [41][42][43] as an analogue of the antithyroidd rug methimazole, [44][45][46] in optoelectronics, [47] as chemicals ensors, [48] and also as ac hemical tool for Pd II extraction from water.…”

Retraction: Synthesis and Characterization of Sterically Congested Mesityltris(imidazolium) Salts and the Corresponding Highly Crystalline Tris‐selone Derivatives

“…[13,25] Imidazole selones, as pecial class of heteroketones, have gained increasing interest in recenty ears as efficient ligating agents in lieu of traditional N-heterocyclic carbenes. In fact, mono-and bis-imidazole selones have been extensively used to generate transitionmetal-based complexes [26][27][28][29][30][31][32][33][34][35][36][37][38] and have furtherb een employed in versatile catalytic applications, such as polymerization [39] and the reduction of nitrobenzenes. [40] Moreover,s uch selenoketones have been used as inhibitors of lactoperoxidase-catalyzed oxidation and tyrosine nitration, [41][42][43] as an analogue of the antithyroidd rug methimazole, [44][45][46] in optoelectronics, [47] as chemicals ensors, [48] and also as ac hemical tool for Pd II extraction from water.…”

Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers

“…A significant deviation from the octahedral bond angles may be indicative of the existence of an inert lone pair, and the largest distortion from the ideal geometry was found for the Cl1–Bi–Cl3 angle in 1A′ : namely, 98.8°. On the basis of a comparison of our system to previously reported structures with stereochemically active 63 , 64 or inactive 65 , 66 bismuth lone pairs, we may consider that the bismuth lone pairs in this study have no appreciable stereochemical activity. The situation is further disturbed by the fact that two different kinds of atoms (S/Cl) coordinate to the bismuth centers, which clearly affects the bonding parameters (bond lengths and bond angles).…”