Dynamic Rotational Motions of Vaulted Chiral trans-Bis(salicylaldiminato)palladium(II) Complexes Bearing Rigid or Flexible Carbon Chain Linkers

被引：10

作者：

Ikeshita, Masahiro ^{[1
]}

Naota, Takeshi ^{[1
]}

机构：

[1] Osaka Univ, Grad Sch Engn Sci, Dept Chem, Toyonaka, Osaka 5608531, Japan

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2018年 / 43期

关键词：

Kinetics; Chirality inversion; Palladium; Macrocyclic ligands; GYROSCOPE-LIKE MOLECULES; METAL-COMPLEXES; HETEROCHIRAL AGGREGATIONS; COPPER(II) COMPLEXES; FLAPPING MOTION; LIGANDS; CRYSTALS; SUBSTITUTION; ENHANCEMENT; ASSOCIATION;

D O I：

10.1002/ejic.201800666

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Planar chiral, trans-bis(salicylaldiminato)palladium(II) complexes having a macrocyclic vaulting structure consisting of either a heptamethylene-butadiynylene-heptamethylene (1) or polymethylene (2) bridge were synthesized and subsequently characterized by NMR, IR, high-resolution mass spectrometry, and single crystal XRD. The dynamic rotational behaviors of these vaulted complexes resulting from a skipping-rope-like molecular motion were examined on the basis of kinetic studies of the racemization of the optically pure (100 % ee) complexes. The chiral inversion rate was found to be significantly affected by the conformational flexibility of the complexes, which in turn could be controlled by adjusting the linker length, the linker rigidity, and the ligation properties of the solvent.

引用

页码：4689 / 4695

页数：7

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