T. Takayama et al., STRUCTURAL-ANALYSIS OF CADMIUM-GLYCYLGLYCINE COMPLEXES STUDIED BY X-RAY-DIFFRACTION AND HIGH-RESOLUTION CD-113 AND C-13 SOLID-STATE NMR, Bulletin of the Chemical Society of Japan, 69(6), 1996, pp. 1579-1586
Structural analysis of bis(glycylglycinato)cadmium(II) complexes prepa
red to adjust the pH to 6 (A) and 9 (C), were studied by X-ray diffrac
tion and high resolution Cd-113 and C-13 solid State NMR. In order to
compare with the structure of A, structural analysis of bis(glycylglyc
inato)zinc(II) complexes (B) prepared to adjust the pH to 6 was also p
erformed by the same methods. The structure of A was six coordinate; a
five-membered chelate ring was formed between the terminal amino-grou
p and the adjacent O (peptide) and the terminal carboxygroups of the d
ipeptide ligands were involved in Cd binding in the complex. The struc
ture of B was similar to A, indicating that the Cd nucleus was better
suited for probing the Zn nucleus-ligand structure. The structure of C
was six coordinate; the four terminal carboxygroups (O) and the two t
erminal aminogroups (N) of the dipeptide ligands were involved in Cd b
inding in the complex. High-resolution Cd-113 and C-13 CP/MAS NMR spec
tra have been measured in order to obtain detailed information about t
he structures. The Cd-113 signal of A showed a low field chemical shif
t compared with the peak of C. This means that the chelate ring shows
decreased shielding. From the C-13 spectra of A and C, it was seen tha
t the Cd nucleus of A is bonded to a carbonyl oxygen (peptide) and the
terminal carboxyl group of the dipeptide, but that for C is not bonde
d to a carbonyl oxygen (peptide).