title: 2-pyrrolylthiones as monoanionic bidentate N,S-chelators: synthesis and molecular structure of 2-pyrrolylthionato complexes of nickel(II), cobalt(III), and mercury(II).
abstract: The metal-chelating ability of 2-pyrrolylthiones is described. The readily available ligands di-2-pyrrolyl thione (6), 2-thioacetylpyrrole (10), and 2-thiobenzoylpyrrole (11) constitute examples of monoanionic ligands with N,S-donor atom sets, although di-2-pyrrolyl thione (6) could theoretically also achieve chelation through an N,N-donor set. A square planar Ni(II) complex, 14, an octahedral Co(III) complex, 18, and a tetrahedral Hg(II) complex, 17, with the di-2-pyrrolyl thionato chelate have been prepared, and their structures have been characterized by 1H NMR, UV-vis, MS, IR, elemental analysis, and single-crystal X-ray diffraction. Crystal data for 14: C18H14N4NiS2.0.28H2O, trigonal, R3, a = 18.467(1) A, b = 18.467(1) A, c = 26.404(2) A, V = 7797(1) A3; Z = 18, R = 3.2%. Crystal data for 18-mer: C27H21CoN6S3.C3H6O (acetone), monoclinic, P21/n, a = 9.569(1) A, b = 23.152(1) A, c = 13.659(1) A, beta = 100.882(8) degrees, V = 2971.6(5) A3, Z = 4, R = 4.3%. Crystal data for 17: C18H14HgN4S2, triclinic, P1, a = 8.443(2), b = 14.278(1) A, c = 7.445(1) A, alpha = 90.561(9) degrees, beta = 97.64(1) degrees, gamma = 104.250(9) degrees, V = 861.3(2) A3, Z = 2, R = 4.2%. The bond lengths and angles of these metal complexes are comparable to those of known N,S-chelates. A comparison of the structural parameters of the ligand in the metal complexes with those for the free ligand 6 demonstrates the preorganization of the free ligand for complexation and demonstrates the spectator role of the noncoordinating pyrrolic unit. Chelation of Ni(II) by 2-thioacetylpyrrole (10) and 2-thiobenzoylpyrrole (11) to provide complexes 12 and 13 with structures analogous to complex 14 is also described.
authors.affiliation: Department of Chemistry, University of Connecticut, 55 North Eagleville Road, U-60, Storrs, Connecticut 06269, USA. bruckner@nucleus.chem.uconn.edu
authors.forename: C
authors.initials: C
authors.lastname: Brückner
authors.forename: S J
authors.initials: SJ
authors.lastname: Rettig
authors.forename: D
authors.initials: D
authors.lastname: Dolphin
mesh_terms: D002614:Chelating Agents / Q000138:chemical synthesis / Q000737:chemistry*; D003035:Cobalt; D018360:Crystallography, X-Ray; D008024:Ligands; D008628:Mercury; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009532:Nickel; D011758:Pyrroles / Q000138:chemical synthesis / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013871:Thiones / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D002614:Chelating Agents; D008024:Ligands; D011758:Pyrroles; D013871:Thiones; D003035:Cobalt; D009532:Nickel; D008628:Mercury