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Structural and Chiroptical Properties of Acyclic and Macrocyclic 1,5‐Bis(oxazoline) Ligands and Their Copper(I) and Silver(I) Complexes
Author(s) -
Hollosi Miklos,
Majer Zsuzsa,
Vass Elemér,
Raza Zlata,
Tomišić Vladislav,
Portada Tomislav,
Piantanida Ivo,
Žinić Mladen,
Šunjić Vitomir
Publication year - 2002
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 - 10.1002/1099-0682(200207)2002:7<1738::aid-ejic1738>3.0.co;2-o
Subject(s) - chemistry , stereocenter , acetonitrile , ligand (biochemistry) , oxazoline , stereochemistry , copper , chromophore , crystallography , titration , stoichiometry , photochemistry , enantioselective synthesis , inorganic chemistry , organic chemistry , biochemistry , receptor , catalysis
C 2 ‐symmetric acyclic ligands 1a − 1e , macrocyclic ligands 2a − 2d and 3 , and their copper(I) and silver(I) complexes were studied by UV, NMR and CD spectroscopy. The stability constants of the metal− 1a and − 1b complexes with 1:1 and 1:2 stoichiometries in acetonitrile were determined by spectrometric titrations. Evidence of tetrahedral coordination for complex [Ag( 1a ) 2 ] + was obtained from the complexation induced shifts (CIS) and NOEs, and corroborated by molecular modeling. Ligands with phenyl rings on the stereogenic centers ( 1a , c and 2 ) exhibit a strong Cotton effect (CE) in the region of the 1 B b band, which is absent in the ligands with benzyl groups on the stereogenic center ( 1b , 3 ). This effect is ascribed to the exciton coupling (EC) of two aromatic chromophores on the stereogenic center. For ligands 1a and 2a the EC changes the sign on complexation to Cu + , revealing opposite helicity of the free and complexed ligand. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)