Sains Malaysiana 36(1): 15-20 (2007)

 

 

Gadolinium(III) Complexes with Dialkyldithiocarbamates

and 1,10-Phenantroline

(Kompleks Gadolinium(III) dengan Dialkilditiokarbamat dan 1, 10 Fenantrolina)

 

 

Indah Raya, Ibrahim Baba, Bohari Mohd Yamin & Djulia Onggo

School of Chemical Sciences & Food Technology

Faculty of Science and Technology, Universiti Kebangsaan Malaysia

43600 Bangi, Selangor, D.E. Malaysia

 

 

ABSTRACT

 

A new series of gadolinium complexes with mixed ligands, dialkyl dithiocarbamate and 1,10-Phenantroline were successfully synthesized using “in situ” methods. Microelemental analysis data of complexes are in agreement with the general formula Gd[S2CNR’R”]3Phen (R’ = ethyl, methyl; R” = butyl, heptyl, isopropyl, isobutyl, benzyl and cyclohexyl; Phen = 1,10-phenantroline). These complexes have been characterized using elemental analysis, infrared, thermogravimetric analysis, conductivity and magnetic measurements. Infrared spectra of complexes showed the thioureide n(C-N) bands were in the region of 1450 - 1490 cm-1. The single n(C-S) bands appeared in the region of 959 – 1003 cm-1 and n(C-H) bands in the region of 2853-2931 cm-1. The crystal structure of tris(N,N-methylbenzyldithiocarbamate)(1,10-phenantroline) gadolinium(III) adopts a triclinic system (space group Pī) with a distorted dodecahedron geometry with a = 11.04(6) Å ,  b = 12.65(7) Å, c = 17.13(10) Å, a =73.86o(8) b =74.54o(8) g = 72.34o(8) and Z = 2. Three dithiocarbamates and one phenanthroline ligands were coordinated to the central Gd atom in bidentate manner.

 

Keywords: Gadolinium; dithiocarbamate; crystal structure

 

 

ABSTRAK

 

Satu siri kompleks logam gadolinium baru dengan dialkilditiokarbamat dan 1,10-fenantrolin telah berjaya disintesis secara “in-situ”. Hasil analisis  bersetuju dengan formula umum Gd[S2CNR’R”]3Phen (R’ = metil, etil; R” = butil, heptil, isopropil, isobutil, benzil dan sikloheksil; Phen = fenantrolina). Kompleks telah diciri dengan analisis unsur, spektroskopi inframerah, analisis termogravimetri, pengukuran kemagnetan dan pengukuran konduktiviti. Spektrum inframerah kompleks menunjukkan jalur tioureida n(C-N) berada di sekitar 1450-1490 cm-1, Manakala jalur tunggal n(C-S) pula berada di kawasan 959-1003 cm-1 dan jalur n(C-H) berada di kawasan 2853-2931 cm-1. Struktur hablur tris(N,N-metilbenzilditiokarbamat)(1,10-fenantrolin)gadolinium(III) menunjukkan sistem hablur triklinik (kumpulan ruang Pī) dengan geometri dodekahedron terherot dengan a = 11.04(6) Å,  b = 12.65(7) Å, c = 17.13(10) Å, a =73.86o(8) b =74.54o(8) g = 72.34o(8) and Z = 2. Tiga molekul ditiokarbamat dan satu molekul fenantrolina memebentuk ikatan kelat kepada atom Gd  secara bidentat.

 

Kata kunci: Gadolinium; ditiokarbamat; struktur hablur

 

 

 

 

 

RUJUKAN/REFERENCES

 

Brown, D. A., Glass, W. K. & Burke, M. A. 1976. The general use of IR spectral criteria in disscussions of the bonding and structure of metal dithiocarbamate. Spectrochem. Acta 32A:137-143.

Coucouvanis, D. & Fackler, J. P. Jr. 1976. Square-planar sulphur complexes. Inorganic Chem. 6: 2047-2053.

Criado, J. J., Fernandez, I. & Macias, B. 1990. Novel chelates of Pd(II) dithiocarbamates, spectroscopic studies and thermal behaviour. Inorg. Chem. Acta 174:67-75

Haas, W. & Schwarz, T. 1963. NH4 diethanol dithiocarbamate a reagent for the spectrophotometric determination of Mo and U. Microchem. Ichonal. Acta 58: 253-259.

Hursthouse, M. B., Malik, M. A., Motervalli, M. & O’Brien, P. 1992. The crystal and molecular structure of N,N-dimethyldiselenocarbamatocadmium(II): cadmium and zinc dimethyldiselenocarbamates as precursors for selenides.
Polyhedron 11: 45-48.

Nomura, R., Takabe, A., & Matsuda, H. 1987. Facile synthesis of antimony dithiocarbamate complexes. Polyhedron 6: 411-416.

Sharma, H., Watanabe, H., Tamura, H., Yasui, H., Matsushita, R. & Takada, J. 1998. Insulin-mimetic vanadyl-dithiocarbamate complexes. Inorg. Chim. Acta 283: 175-183.

Sheldrick, G. M. 1996. SAINT V4, Software reference manual, Siemens Analytical X-ray System, Madison, WI, USA.

Sheldrick, G. M. 1996. SADABS, Program for Empirical Absorption Correction of Area Detector Data, University of Gottingen, Germany.

Sheldrick, G. M. 1997. SHELXTL V 5.1, Software reference manual, Bruker AXS, Inc., Madison, WI, USA.

Siddal, T. H. & Steward, W. E. 1970. Preparation and studies of magnetic and spectroscopic properties of alkyl ammonium lanthanide tetrakis (N,N-dialkyldithiocarbamates). J. Inorg.Nuclear Chem. 32: 1147-1158.

Siemens, 1996, SMART and SAINT. Area Detector Control and Integration Software. Siemens Analytical X-Ray Systems, Inc., Madison, Wisconsin, USA.

Su, C., Tan, M., Tang, N., Gan, X. & Liu, W.  1997. Synthesis, structure and spectroscopic properties of dimmethylammonium lanthanide tetrakis(N, N-dimmethyldithiocarbamate). Polyhedron  16: 1643-1650.

Tang, N., Zhu, H., Tan, M., Gan, X. & Wang, A. 1991. Synthesis and characterisation of dimethylammonium lanthanide (monomethyldithiocarbamate). Polyhedron 16:1643-1650            .

Thorn, G.D., & Ludwig, R.A., 1962. The dithiocarbamates abd related compounds. New York:  Elsevier Pub.Co.

Venkatachalam, V., Ramalingam, K., Casellato, U. & Graziani, R. 1997. Structural and electronic effect of alkyl substituents on the main group dithiocarbamato complexes: crystals and molecular structures of tris(N,N’-iminodiethanoldithiocarbamato)metal(III) complexes (M = As, Sb and Bi) and cyclic voltammetric studies on substituted dithiocarbamates. Polyhedron 16(7): 1211-1221.

Zhu, H., Tang, N., Gan, X., Wang, A. & Tan, M. 1993. Synthesis and characterization of light lanthanide piperidinocarbodithioate complexes. Polyhedron 12: 945-991.

 

 

 
previous