Solid State and Solution Characterization of Chiral, Conformationally Mobile Tripodal Ligands

James Canary, Craig S. Allen, Jesus M. Castagnetto, Yu Hung Chiu, Paul J. Toscano, Yihan Wang

Research output: Contribution to journalArticle

Abstract

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-MePh 2TPA), 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 C 3-symmetric complexes with Zn II and Cu II salts that possess an available electrophilic coordination site. Xray crystallographic structures of the complexes [Zn(α-MeTPA)Cl](ClO 4), [Zn(α-MeBQPA)Cl](ClO 4), and [Zn(α-PhTPA)Cl](ClO 4) 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.

Original languageEnglish (US)
Pages (from-to)6255-6262
Number of pages8
JournalInorganic Chemistry
Volume37
Issue number24
StatePublished - 1998

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solid solutions
Ligands
solid state
ligands
propellers
Propellers
methylene
Salts
salts
rings
Computer simulation
synthesis
estimates
simulation
Temperature
temperature
energy
methylamine
N,N-bis((2-quinolyl)methyl)-1-(2-pyridyl)ethanamine

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Canary, J., Allen, C. S., Castagnetto, J. M., Chiu, Y. H., Toscano, P. J., & Wang, Y. (1998). Solid State and Solution Characterization of Chiral, Conformationally Mobile Tripodal Ligands. Inorganic Chemistry, 37(24), 6255-6262.

Solid State and Solution Characterization of Chiral, Conformationally Mobile Tripodal Ligands. / Canary, James; Allen, Craig S.; Castagnetto, Jesus M.; Chiu, Yu Hung; Toscano, Paul J.; Wang, Yihan.

In: Inorganic Chemistry, Vol. 37, No. 24, 1998, p. 6255-6262.

Research output: Contribution to journalArticle

Canary, J, Allen, CS, Castagnetto, JM, Chiu, YH, Toscano, PJ & Wang, Y 1998, 'Solid State and Solution Characterization of Chiral, Conformationally Mobile Tripodal Ligands', Inorganic Chemistry, vol. 37, no. 24, pp. 6255-6262.
Canary J, Allen CS, Castagnetto JM, Chiu YH, Toscano PJ, Wang Y. Solid State and Solution Characterization of Chiral, Conformationally Mobile Tripodal Ligands. Inorganic Chemistry. 1998;37(24):6255-6262.
Canary, James ; Allen, Craig S. ; Castagnetto, Jesus M. ; Chiu, Yu Hung ; Toscano, Paul J. ; Wang, Yihan. / Solid State and Solution Characterization of Chiral, Conformationally Mobile Tripodal Ligands. In: Inorganic Chemistry. 1998 ; Vol. 37, No. 24. pp. 6255-6262.
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abstract = "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-MePh 2TPA), 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 C 3-symmetric complexes with Zn II and Cu II salts that possess an available electrophilic coordination site. Xray crystallographic structures of the complexes [Zn(α-MeTPA)Cl](ClO 4), [Zn(α-MeBQPA)Cl](ClO 4), and [Zn(α-PhTPA)Cl](ClO 4) 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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