Solid State And Solution Characterization Of Chiral, Conformationally Mobile Tripodal Ligands
INORGANIC CHEMISTRY(1998)
Abstract
The synthesis of the ligands N,N-bis[(2-pyridyl)methyl]-1-(2-pyridyl)ethanamine (1, alpha-MeTPA), N,N-bisl[6-phenyl-2-pyridyl)methyl]-1-(2-pyridyl)ethanamine (2, alpha-MePh(2)TPA), N,N-bis[(2-quinolyl)methyl]-1-(2-pyridyl)ethanamine, (3, alpha-MeBQPA), and N,N-bis[(2-pyridyl)]methyl(phenyl)(2-pyridyl)methanamine (4, alpha-PhTPA) is described. The ligands form chiral, pseudo C-3-symmetric complexes with Zn-II and Cu-II salts that possess an available electrophilic coordination site. X-ray crystallographic structures of the complexes [Zn(alpha-MeTPA)Cl] (ClO4), [Zn(alpha-MeBQPA)Cl](ClO4), and [Zn(alpha-PhTPA)Cl](ClO4) show that the spatial arrangement of the three pyridyl groups resembles a propeller whose directional sense is controlled by a substituent on one methylene arm. Chiroptical measurements provide supporting information that the complexes maintain similar structures in solution. Monte Carlo/stochastic dynamics (MC/SD) simulations of the [Zn(L)Cl](+) complexes indicate that only two conformers are populated at normal temperatures, suggest the presence of a synchronicity in the movement of the heteroaromatic rings during conformer interconversions, and provide an estimate of the energy difference between the conformers.
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Key words
ligands,chiral
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