Structural and chiroptical properties of acyclic and macrocyclic 1,5-bis(oxazoline) ligands and their copper(I) and silver(I) complexes

被引:0
作者
Hollosi, M
Majer, Z
Vass, E
Raza, Z
Tomisic, V
Portada, T
Piantanida, I
Zinic, M
Sunjic, V
机构
[1] Eotvos Lorand Univ, Dept Organ Chem, H-1518 Budapest, Hungary
[2] Rudjer Boskovic Inst, Dept Organ Chem & Biochem, Zagreb 10002, Croatia
[3] Univ Zagreb, Fac Sci, Phys Chem Lab, Zagreb 10001, Croatia
关键词
circular dichroism; conformation analysis; copper; silver; bis(oxazoline) ligands; macrocyclic ligands;
D O I
10.1002/1099-0682(200207)2002:73.0.CO;2-O
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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 B-1(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 la and 2a the EC changes the sign on complexation to Cu+, revealing opposite helicity of the free and complexed ligand.
引用
收藏
页码:1738 / 1748
页数:11
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