A1 Refereed original research article in a scientific journal
Substituent-controlled preference of carbonyl group-metal coordination in d(8) metal complexes with non-symmetric pentadentate ligands. Structural and stereochemical aspects
Authors: Jianlin Han, Taizo Ono, Hidehiro Uekusa, Karel D. Klika, Vadim A. Soloshonok
Publisher: ROYAL SOC CHEMISTRY
Publishing place: CAMBRIDGE; THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND
Publication year: 2014
Journal: Dalton Transactions
Journal name in source: Dalton Transactions
Journal acronym: Dalton Trans.
Volume: 43
Issue: 14
First page : 5375
Last page: 5381
Number of pages: 7
ISSN: 1477-9226
DOI: https://doi.org/10.1039/c3dt53312c
Chirally switchable Ni(II) and Pd(II) complexes were synthesized and fully characterized by X-ray crystallography and additionally by spectroscopic means (NMR and MS). The syntheses and characterization of their ligands are also reported. It was found that control of the stereochemical preference between (S*,S*) and (S*,R*) diastereomers by substituent modification of the ligand sidearms was possible in the solid state with the preferred atomic coordinations of the sidearms consistent with expectations based on the electron-withdrawing properties of the substituent-o-CF3 group. The dilemma arising in terms of assigning the absolute configuration descriptors resulting from selecting between strictly following only the covalent bonds of the ligand and disregarding the nature of the bonds altogether and thus bringing the coordinate bonds into consideration to determine the stereochemical priority sequence is hereby resolved by declaring that the latter option is to be preferred. The results obtained here provide a clear indication that sidearm substitution of the Ni(II) and Pd(II) complexes need not disturb macromolecular stereochemical arrangements leading to quasidiastereomeric relationships. This permits the design of molecular systems sensitive to external stimuli with predictable macromolecular structure.