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Dynamic Rotational Motions of Vaulted Chiral trans ‐Bis(salicylaldiminato)palladium(II) Complexes Bearing Rigid or Flexible Carbon Chain Linkers
Author(s) -
Ikeshita Masahiro,
Naota Takeshi
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800666
Subject(s) - chemistry , racemization , palladium , atropisomer , planar chirality , linker , crystallography , stereochemistry , enantioselective synthesis , organic chemistry , catalysis , computer science , operating system
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.