The effect of steric bulk on coordination sphere geometry for BiCl₃complexes with bulky heterocyclic imidazolethione ligands

Abstract

The synthesis and characterization of three new complexes, BiCl 3 (mipit) 2 , BiCl 3 (emit) 2 and BiCl 3 (mnpit) 2 are reported where emit ¼ 1-ethyl-3-methyl-2(3H)-imidazolethione; mnpit ¼ 1-methyl-3-(1-propyl)-2(3H)-imidazolethione;mipit ¼ 1-methyl-3-(2-propyl)-2(3H)-imidazolethione. X-ray crystallographic results are reported for the mnpit and mipit complexes whereas the structure of the emit complex is under reinvestigation because of disorder. BiCl 3 (mnpit) 2 crystallizes in a triclinic space group (P1) with lattice parameters: a ¼ 9.4223(6) Å , b ¼ 10.6275(6) Å , c ¼ 12.8860(8) Å , a ¼ 108.329(1)8, b ¼ 90.388(1)8, g ¼ 115.200(1)8, V ¼ 1093(1) Å 3 , Z ¼ 2. BiCl 3 (mipit) 2 crystallizes in a triclinic space group (P1) with lattice parameters: a ¼ 10.4347(8) Å , b ¼ 11.0018(9) Å , c ¼ 11.2075(9) Å , a ¼ 95.827(1)8, b ¼ 104.890(1)8, g ¼ 117.064(1)8, V ¼ 1071(1) Å 3 , Z ¼ 2. Both complexes show the same pattern with two BiL 2 Cl 4 (L ¼ ligand) octahedra sharing a common edge through bridging chlorine atoms and the ligands occupying trans positions perpendicular to the plane made by the two bismuth atoms and six chlorine atoms. No strong evidence for a hemidirected lone pair is observed in either of the two complexes.

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

“…The S1-Bi1-O1 angle of 176.2(2)° deviates slightly from linearity. The coordination behavior of 1,3-dialkylimidazole-2-thiones toward BiCl 3 and resulting mononuclear and dinuclear complexes have been described by Williams et al [11]. The authors reported dinuclear compounds of the type [Bi(imt) 2 (µ-Cl)Cl 2 ] 2 , from imt ligands and from a N-substituted imidazole-2-thione ligand [9], which are structurally related to complex 2.…”

“…The authors reported dinuclear compounds of the type [Bi(imt) 2 (µ-Cl)Cl 2 ] 2 , from imt ligands and from a N-substituted imidazole-2-thione ligand [9], which are structurally related to complex 2. It is interesting to note that the two M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 11 identical Bi-S bond distances of 2.703(2) Å in complex 2 are considerably shorter than those reported in these works, where they range from 2.750(1) to 2.937(1) Å. Although shorter Bi-S bonds have been observed in scorpionate tris(imidazole-2-thione) complexes of Bi(III) [17,19,20], those observed in 2 are in the lower range for this bond.…”

“…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).…”

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

“…[1][2][3][4][5][6][7][8][9][10][11][12] With an increasei nt he orbitals ize of the chalcogens (O 2p, S3p, Se 4p, and Te 5p), the stability of the corresponding ketones gradually decreases owing to improper orbitalo verlap with carbon (C 2p). [13] Rationally,e xamples of chalcogenone monomers progressivelyd ecrease from Ot oT e. As am atter of fact, monomeric tellurones are extremelyr are, [14,15] whereas similar oxonesa nd thionesa re quite common in nature and in synthesis laboratories.…”

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

“…[1][2][3][4][5][6][7][8][9][10][11][12] With an increasei nt he orbitals ize of the chalcogens (O 2p, S3p, Se 4p, and Te 5p), the stability of the corresponding ketones gradually decreases owing to improper orbitalo verlap with carbon (C 2p). [13] Rationally,e xamples of chalcogenone monomers progressivelyd ecrease from Ot oT e. As am atter of fact, monomeric tellurones are extremelyr are, [14,15] whereas similar oxonesa nd thionesa re quite common in nature and in synthesis laboratories.…”