Ligand Synthesis and Coordination Chemistry

We are interested in synthesizing multidentate ligands that self-assemble into supramolecular structures in the presence of late transition metal ions.

We have prepared a series of multidentate pyridine-containing ligands in order to examine the relationship between ligand structure and metal complex geometry. The ligands, some of which contain silicon, vary in terms of flexibility and spatial orientation of the pyridyl groups.

Two examples, which complex with Ag(I) to form dimers, are shown below to the left. The complex between the disilane ligand and AgOTf is shown to the right (an interactive Jmol structure). We found that related ligands in the series also complex to Cu(II) and Pd(II) (unpublished).

  • Sengupta, P.; Zhang, H.; Son, D. Y. "Spacer Flexibility in Bis(pyridyl)-ligands: Chelating Organosilicon Pyridylethynyl Ligands.", Inorganic Chemistry 2004, 43, 1828-1830. Link

We also prepared a series of bis(pyridyl)esters and ethers and their corresponding complexes with Ag(I), Cu(II), Co(II). One ligand example is shown below along with its corresponding complex with AgNO3. Note the single-stranded helical structure of the complex.

  • Siaw-Lattey, C.; Zhang, H.; Son, D. Y. "Synthesis and Characterization of a Versatile Bis(pyridylether) Ligand and Its Complexes with Ag(I), Cu(II), and Co(II).", Polyhedron 2005, 24, 785-790. Link

  • Kalra, M. K.; Zhang, H.; Son, D. Y. “Helical Metallopolymers from the Coordination of New Bis(pyridyl)terephthalate Ligands with Silver(I).”, Inorganic Chemistry Communications 2004, 7, 1019-1022. Link

We have synthesized and characterized a large number of other multidentate ligands containing pyridine and other hetaryl groups. Many of these ligands bind readily to late transition metals.

  • Sengupta, P.; Henkes, A. E.; Kumar, M. K.; Zhang, H.; Son, D. Y. "A General One-Step Synthesis of Multidentate (Pyridylalkyl)amines from Mono-, Bis-, Tris- and Tetrakis(bromomethyl)benzenes: Potential Ligands for Supramolecular Assembly", Synthesis 2008, 79-86. Link

  • Gondi, S. R.; Son, D. Y. "Synthesis of (Hetaryl)alkylamines from the Reactions of 2-Aminopyrimidine, 2-Aminothiazole, and 2-Aminothiazoline with Benzyl Bromide and Xylylene Dibromides", Synthetic Communications 2008, 38, 401-410. Link

  • Zhang, H.; Gondi, S. R.; Son, D. Y. "Poly[μ3-1,3-dithiolane-2-methanol-κ3S:S:S'-μ-nitrato-silver(I)]", Acta Crystallographica Section E 2006, E62, m3086-m3088. Link

  • Zhang, H.; Gondi, S. R.; Son, D. Y. "Poly[bis(μ3-benzyloxyiminoacetato)nitratotrisilver(I)]", Acta Crystallographica Section E 2006, E62, m1613-m1615. Link

  • Gondi, S. R.; Son, D. Y. "Cholane Derivatives with Potential Ligating Groups at the 3- and 24-Positions.", Synthetic Communications 2006, 36, 1317-1331. Link

  • Gondi, S. R.; Son, D. Y. "Mono-, Bis-, and Tris-1,3-dithiolane Aromatic Derivatives by Esterification and Amidation Reactions.", Journal of Sulfur Chemistry 2005, 26, 13-19. Link

  • Gondi, S. R.; Son, D. Y. “Synthesis of N,N-bis(2-Thiazolinyl)-, N,N-bis(2-Thiazolyl)-, and N,N-bis(2-Pyrimidinyl)-Benzene Dicarboxamides.”, Synthetic Communications 2004, 34, 3061-3072. Link

We recently synthesized a series of silyl-substituted thioether ligands that display remarkable versatility in binding to Ag(I). We have characterized a total of nine Ag(I)-complexes with these ligands, several of which display argentophilic interactions. Two examples of these ligands and their corresponding complexes with Ag(I) are shown below.

  • Rim, C.; Zhang, H.; Son, D. Y. "Silyl-substituted thioether ligands and their Ag(I) complexes", Inorganic Chemistry 2008, 47, 11993-12003. Link