Borate-based ligands with two soft heterocycle/thione groups and their sodium and bismuth complexes

Abstract

Two novel sodium complexes [NaBb] (1) (Bb = dihydrobis(2-mercapto-benzimidazolyl)borate) and [NaBt(Me)] (2) (Bt(Me) = dihydrobis(2-mercapto-4-methylthiazolyl)borate) have been prepared and characterized by using two heterocycles, 2-mercapto-benzimidazole and 2-mercapto-4-methylthiazole, as well as NaBH4 as precursors. The dipodal boron centred soft ligands Bb and Bt(Me) were prepared in situ. The reactivity of [NaBb] (1) and [NaBt(Me)] (2) towards Bi(III) ions has been studied. The resulting complex [BiBb2Cl] (3) contains an MS4 core with κ(3)-S,S,H coordination mode, while the complex [BiBt(Me)3] (4) with an MS6 core adopts a coordination mode κ(2)-S,S. A reaction of BiCl3 with the heterocyclic precursors 2-mercapto-benzimidazole (L(1)) and 2-mercapto-4-methylthiazole (L(2)) was also attempted; this afforded the monomeric [BiL(1)4Cl2][BiL(1)2Cl4] (5) and dimeric [BiL(2)2(μ-Cl)Cl]2 (6) bismuth complexes. The bismuth complexes possess distorted octahedral geometries except 3 for which a face-capped octahedron is found. The presence of (B)H···Bi interactions has been identified by X-ray diffraction in 3 with a H···Bi distance of 2.58(1) Å which is uniquely short and unprecedented. Two of the synthesized complexes (4 and 5) have been investigated by luminescence spectroscopy. They feature emission bands in the solid state at room temperature at 674 (4) and 586 nm (5), which are hypsochromically shifted in (frozen) ethanolic solutions at 77 K to 618 and 537 nm, respectively.

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

“…Although 1 has been reported in the literature [43], no analytical data are available so far. The 1 H and 13 The molecular structure of 2 shows a dinuclear Bi(III) complex that crystallizes in the space group P2 1 /c. Both metal ions adopt a slightly distorted octahedral coordination geometry and the corresponding polyhedra share a common edge via two bridging iodido ligands.…”

“…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). Likewise, Bi(III) complexes of the related thiolates of triazoles [21] and tetrazoles [22] have been reported.…”

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.…”