TY - JOUR
T1 - Novel CdCl2 and HgCl2 complexes with 3-monosubstituted and 3,3-disubstituted 1-furoylthioureas
T2 - IR and Raman spectra
AU - Estévez-Hernández, O.
AU - Otazo-Sánchez, E.
AU - Cisneros, J. L.Hidalgo Hidalgo de
AU - Naranjo-Rodríguez, I.
AU - Reguera, E.
N1 - Funding Information:
O.E.H. thanks Faculty of Sciences (University of Cadiz, Spain), through its PhD program, the access to experimental facilities. E.R. acknowledges the financial support provided by CLAF to carry out research activities on molecular materials. E.O.S acknowledges PROMEP project given by Hidalgo State Autonomous University (Mexico). The authors thank C. Vazquez from IIM (UNAM, Mexico) for TGA data acquisition.
PY - 2006/7
Y1 - 2006/7
N2 - Two series of coordination complexes of CdCl2 and HgCl2 with 3-monosubstituted and 3,3-disubstituted 1-furoylthioureas were prepared and characterized. These complexes were obtained with a medium to high yield from ethanolic solutions of both ligand and salt. The formed complex results from the salt-ligand interaction with participation of both the salt anion and cation. Information on the coordination chemistry of these complexes was derived from thermal stability data, and IR, Raman and 13C CPMAS NMR spectra. On coordination the electronic structure of these ligands changes as a whole, affecting practically all their vibrational pattern, however, within that complex pattern some vibrations provide valuable information on the nature of the studied complexes. These thiourea derivatives behave as neutral ligands, which coordinate the metal ion through the sulfur atom of the thiocarbonyl group. This fact is supported by the observed frequency shift, to lower values, in the ν(CS) vibration on the coordination and the appearance of a low frequency Raman line which was assigned to the metal-sulfur stretching, ν(M-S), in the formed complex. The frequency of the ν(CO) vibration always increases on complex formation, which discards the participation of the carbonyl group in the coordination process. The complexation takes place preserving the free ligand conformation, established from intra-molecular interactions, particularly in 3-monosubstituted ligands. Such features of the studied ligands and their complexes are also supported by 13C CPMAS NMR spectra. This spectroscopic information correlates with the reported behavior of the ligands in ion selective electrodes.
AB - Two series of coordination complexes of CdCl2 and HgCl2 with 3-monosubstituted and 3,3-disubstituted 1-furoylthioureas were prepared and characterized. These complexes were obtained with a medium to high yield from ethanolic solutions of both ligand and salt. The formed complex results from the salt-ligand interaction with participation of both the salt anion and cation. Information on the coordination chemistry of these complexes was derived from thermal stability data, and IR, Raman and 13C CPMAS NMR spectra. On coordination the electronic structure of these ligands changes as a whole, affecting practically all their vibrational pattern, however, within that complex pattern some vibrations provide valuable information on the nature of the studied complexes. These thiourea derivatives behave as neutral ligands, which coordinate the metal ion through the sulfur atom of the thiocarbonyl group. This fact is supported by the observed frequency shift, to lower values, in the ν(CS) vibration on the coordination and the appearance of a low frequency Raman line which was assigned to the metal-sulfur stretching, ν(M-S), in the formed complex. The frequency of the ν(CO) vibration always increases on complex formation, which discards the participation of the carbonyl group in the coordination process. The complexation takes place preserving the free ligand conformation, established from intra-molecular interactions, particularly in 3-monosubstituted ligands. Such features of the studied ligands and their complexes are also supported by 13C CPMAS NMR spectra. This spectroscopic information correlates with the reported behavior of the ligands in ion selective electrodes.
KW - CdCl and HgCl complexes
KW - Furoylthioureas
KW - IR
KW - Raman
KW - Thiourea derivative complexes
UR - http://www.scopus.com/inward/record.url?scp=33747061886&partnerID=8YFLogxK
U2 - 10.1016/j.saa.2005.09.005
DO - 10.1016/j.saa.2005.09.005
M3 - Artículo
C2 - 16330247
SN - 1386-1425
VL - 64
SP - 961
EP - 971
JO - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
JF - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
IS - 4
ER -