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Effects of structures of HgX(2) complexes (X = CF(3)SO(3) and Cl) with chiral bidentate ligands on circular dichroism spectra.
MedLine Citation:
PMID:  23280359     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The effects of the structures of HgX(2) complexes (X = CF(3)SO(3) and Cl) with chiral bidentate ligands [(R)-(-)-1-(1-naphthyl)-N,N-bis(pyridin-4-ylmethyl)ethanamine, (R)-(+)-1-phenyl-N,N-bis(pyridin-4-ylmethyl)ethanamine, (R)-(-)-1-(1-naphthyl)-N,N-bis(pyridin-3-ylmethyl)ethanamine, and (R)-(+)-1-phenyl-N,N-bis(pyridin-4-ylmethyl)ethanamine] on circular dichroism (CD) spectra are reported. The CD spectra of free (R)-(-)- and (R)-(+)-, which have 4-pyridyl groups, are similar to those of (R)-(-)- and (R)-(+)-, which have 3-pyridyl groups. When equimolar amounts of Hg(CF(3)SO(3))(2) are added to these ligands, a decrease in the CD intensity of (R)-(-)- is observed, and significant spectral changes (intensity and shape) are observed in (R)-(-)-, (R)-(+)-, and (R)-(+)-. X-ray crystal structures suggest that the (R)-(-)-/Hg(CF(3)SO(3))(2) complex is a coordination polymer with no bridging CF(3)SO(3) anions, whereas the (R)-(-)-/Hg(CF(3)SO(3))(2) and (R)-(+)-/Hg(CF(3)SO(3))(2) complexes are coordination polymers with CF(3)SO(3) anion bridges, and the (R)-(+)-/Hg(CF(3)SO(3))(2) complex has a tricyclic structure bridged by CF(3)SO(3) anions. Two different conformers, which have clockwise and counter-clockwise screw senses between the naphthalene axis and the pyridine axis, are observed in the ligand components of the (R)-(-)-/Hg(CF(3)SO(3))(2) complex. In contrast, the X-ray structures of the (R)-(-)-/HgCl(2) and (R)-(+)-/HgCl(2) complexes are one-dimensional coordination polymers without bridging Cl anions. The significant CD spectral changes in the HgX(2) complexes with different chiral bidentate ligands require formation of rigid structures and a single-directional screw sense between chromophores.
Authors:
Mari Ikeda; Shunsuke Kuwahara; Shim Sung Lee; Yoichi Habata
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-2
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-2     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Department of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan. habata@chem.sci.toho-u.ac.jp.
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