The Pd(II) complexes of thiacalixaniline (TCAn) and thiacalixarene (TCAr), in which four aniline and phenol units are linked by four sulfides at the o,o′-positions, respectively, were prepared by simply heating the ligands with Pd(II)(OAc)2 in CHCl3 or benzene at reflux and structurally characterized by X-ray diffraction methods. In TCAn, two thiacalix ligands adopting a pinched-cone conformation are fused at the narrower rims to coordinate to two Pd(II) ions by amide NH- and the adjacent S atoms. In contrast for TCAr, two ligands coordinate to two Pd(II) ions with phenolate O- and thioether S atoms at the narrower rims. Four sets of hydrogen bonding between the O- and free OH cause a deviation of the Pd(II) centers from the square coordination plane and also lead the conformation of the calix to be more cone-like to provide enough space to accommodate guest CH3CN molecules.
|ジャーナル||Journal of the Chemical Society. Dalton Transactions|
|出版ステータス||Published - 2003 2 21|
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