TY - JOUR
T1 - Solid State and Solution Characterization of Chiral, Conformationally Mobile Tripodal Ligands
AU - Canary, James W.
AU - Allen, Craig S.
AU - Castagnetto, Jesus M.
AU - Chiu, Yu Hung
AU - Toscano, Paul J.
AU - Wang, Yihan
PY - 1998
Y1 - 1998
N2 - The synthesis of the ligands N,N-bis[(2-pyridyl)methyl]-1-(2-pyridyl)ethanamine (1, α-MeTPA), N,N-bis[(6-phenyl-2-pyridyl)methyl]-1-(2-pyridyl)ethanamine (2, α-MePh2TPA), N,N-bis[(2-quinolyl)methyl]-1-(2-pyridyl)ethanamine, (3, α-MeBQPA), and N,N-bis[(2-pyridyl)]methyl(phenyl)(2-pyridyl)methanamine (4, α-PhTPA) is described. The ligands form chiral, pseudo C3-symmetric complexes with ZnII and CuII salts that possess an available electrophilic coordination site. Xray crystallographic structures of the complexes [Zn(α-MeTPA)Cl](ClO4), [Zn(α-MeBQPA)Cl](ClO4), and [Zn(α-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.
AB - The synthesis of the ligands N,N-bis[(2-pyridyl)methyl]-1-(2-pyridyl)ethanamine (1, α-MeTPA), N,N-bis[(6-phenyl-2-pyridyl)methyl]-1-(2-pyridyl)ethanamine (2, α-MePh2TPA), N,N-bis[(2-quinolyl)methyl]-1-(2-pyridyl)ethanamine, (3, α-MeBQPA), and N,N-bis[(2-pyridyl)]methyl(phenyl)(2-pyridyl)methanamine (4, α-PhTPA) is described. The ligands form chiral, pseudo C3-symmetric complexes with ZnII and CuII salts that possess an available electrophilic coordination site. Xray crystallographic structures of the complexes [Zn(α-MeTPA)Cl](ClO4), [Zn(α-MeBQPA)Cl](ClO4), and [Zn(α-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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U2 - 10.1021/ic9803098
DO - 10.1021/ic9803098
M3 - Article
AN - SCOPUS:0000351748
SN - 0020-1669
VL - 37
SP - 6255
EP - 6262
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 24
ER -