M(p-FENİLENDİAMİN)Ni(CN)4.2G (M = Co, Zn, Cd ve G = 1,4-DİKLOROBENZEN) HOFMANN TİPİ KLATRATLARIN SENTEZİ ve YAPISAL ÖZELLİKLERİNİN İNCELENMESİ

Abstract

Bu çalışmada M(p-Fenilendiamin)Ni(CN)4.2G (M = Co, Zn, Cd ve G = 1,4-Diklorobenzen) klatratları ilk kez ve toz olarak elde edildi. Bu klatratların infrared spektrumları (4000 – 400) cm-1 spektroskopik bölgesinde alındı ve soğurma titreşim modları işaretlendi. Bu işaretlemeler bilimsel kaynaklarda yer alan diğer Hofmann-tipi klatratların işaretlemeleri ile karşılaştırıldı ve benzer sonuçlar gözlendi. Bu klatratların termal davranışları, termogravimetrik analiz (TG), diferansiyel termal analiz (DTA) ve diferansiyel termogravimetrik analiz (DTG) yöntemleri ile incelendi. Bu çalışma sonucunda Hofmann-tipi klatratlara üç yeni örnek katılmıştır.

Keywords

• Hofmann-Tipi Klatratlar,İnfrared Spektroskopisi,p-fenilendiamin,Termal Analiz Yöntemleri

THE SYNTHESIS OF M(p-PHENYLENEDIAMINE)Ni(CN)4.2G (M = Co, Zn, Cd and G = 1,4- DICHLOROBENZENE) HOFMANN TYPE CLATHRATES and INVESTIGATION OF THEIR STRUCTURAL PROPERTIES

Abstract

In this study, clathrates of M(p-Phenylenediamine)Ni(CN)4.2G (M = Co, Zn, Cd and G = 1,4-Dichlorobenzene) were obtained in powder form for the first time. The infrared spectra of these clathrates were taken in (4000 - 400) cm-1 spectroscopic range and the absorption vibration modes were assigned. These assignments were compared with those of other Hofmann-type clathrates in the literature and similar results were observed. The thermal behaviors of these clathrates were studied by thermogravimetric analysis (TG), differential thermal analysis (DTA) and differential thermogravimetric analysis (DTG) methods. As a result of this study, three new examples were added to Hofmann-type clathrates.

Keywords

• Hofmann-type clathrates
• Infrared Spectroscopy
• p-Phenylenediamine
• Thermal analysis methods

References

1. [1] Powell, H.M., Rayner, J.H. (1949). Clathrate compounds formed by benzene with an ammonia nickel cyanide complex. Nature, 163, 566-567.
2. [2] Hogan, M.M. (1962). Clathrates and inclusion compounds, Reinhold Publication Corporation, New York.
3. [3] Davies, J.E.D. (1998). Vibrational spectroscopic studies of host-guest compounds. An International Journal for Physical and Engineering Sciences, 51(2), 120-125.
4. [4] Iwamoto, T. (1981). Recent developments in the chemistry of Hofmann-type and the analogous clathrates. Journal of Molecular Structure, 75(1), 51-65.
5. [5] Iwamoto, T. (1996). Past, present and future of the clathrates inclusion compounds built of cyanometallate hosts. Journal of İnclusion Phenomena and Molecular Recognition in Chemistry, 24(1), 61-132.
6. [6] Iwamoto, T., Nakano, T., Morita, M., Miyoshi, T., Miyamoto, T., and Sasaki, T. (1968). The Hofmann-type clathrate: M(NH3)M´(CN)4.2G. Inorganica Chimica Acta, 2, 313-316.
7. [7] Iwamoto, T., Shriver, D. (1972). Benzene clathrates with novel kind of metal complex host lattice, Cd(en)Cd(CN)4.2C6H6 and Cd(en)Cd(CN)4.2C6H6, Inorganic Chemistry, 11(10), 2570-2572.
8. [8] Akalın, E., Akyüz, S. (2000). Theoretical study of IR spectra of paraphenylenediamine, Vibrational Spectroscopy, 22(1), 3-10.

9. [9] Akalın, E., Akyüz, S. (2001). Experimental and theoretical study of the vibrational spectra of paraphenylenediamine transition metal (II) complexes, Journal of Molecular Structure, 563, 579-586.
10. [10] Akyüz, S. (1986). An Infrared and Raman Spectroscopic Investigation of Copper (II) Tetracyanonickelate Complexes of α, -β- and γ-picoline, Journal of İnclusion Phenomena, 28(4), 219-223.
11. [11] Kartal, Z., Ölmez, A. (2005). FT-IR Spectroscopic Study of M(Cyclopentanone)2Ni(CN)4 Complexes (M = Ni, Cd and Co). Zeitschrift für Naturforschung. 60a, 537-540.
12. [12] Kartal, Z. (2009). FT-IR spectroscopic study on some Hofmann-type clathrates: M(p-Benzoquinone)Ni(CN)4.2G (M = Mn, Co, Ni or Hg; G = Aniline), Journal of Molecular Structure, 938(1-3), 70-75.
13. 13] Kartal, Z., Şentürk, Ş. (2005). FT-IR Spectroscopic Study of M(Benzoic Acid)2Ni(CN)4 Complexes (M = Ni, Cd, Co and Mn), Zeitschrift für Naturforschung. 60a, 285-288.
14. [14] McCullough R.L., Jones L.H and Crosby G.A. (1960). An analysis of the vibrational spectrum of the tetracyanonickelate (II) ion in a crystal lattice, Spectrochimica Acta, 16(8), 929-944.
15. [15] Kartal, Z., Sayın, E. (2011). FTIR spectroscopic and thermal study M(Cyclohexanethiol)2Ni(CN)4·(1,4-dioxane) (M = Mn, Co, Ni and Cd), Journal of Molecular Structure, 994(1-3), 170-178.
16. [16] Türköz, D., Kartal, Z. and Bahçeli, S. (2004). FT-IR spectroscopic study of Co(1-Propanethiol)2Ni(CN)4.Benzene Clathrate, Zeitschrift für Naturforschung, 59a, 523-526.
17. [17] Kürkçüoğlu, G.S., Yeşilel, O. Z., Kavlak, İ., Büyükgüngör, O. (2009). Nickel(II)…π interaction in [M(ampy)2Ni(μ-CN)2(CN)2]n (M = Zn (II) and Cd (II), ampy = 2-aminomethylpyridine): Syntheses, vibrational spectroscopy, thermal analyses and crystal structures of cyano-bridged heteronuclear polymeric complexes, Journal of Molecular Structure. 920(1-3), 220-226.
18. [18] Green, J.H.S. (1970). Vibrational spectra of benzene derivatives –VIII m-disubstituted compounds, Spectrochimica Acta, 26A, 1523-1533.
19. [19] Sertbakan, T.R., Sağlam, S., Kasap, E., Kantarcı, Z. (2000). Infrared spectroscopic studies of the Hofmann-dadn-type clathrates: M(1,10- diaminodecane)Ni(CN)4.1,5G (M= Co, Ni or Cd; G= Chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene), Vibrational Spectroscopy, 24, 249-255.
20. [20] Scherer, J.R, Evans, J.C. (1963). Vibrational spectra and assignments for sixteen chlorobenzenes, Spectrochimica Acta, 19, 1739-1775.
21. [21] Kartal, Z., Parlak, C., Şentürk, Ş., Aytekin, M.T., and Şenyel, M. (2007). FT-IR spectroscopic study of the Hofmann-Td-type clathrates: Ni(1,9-diaminononane)M´(CN)4.2G (M´ = Cd or Hg, G = benzene, 1,2-dichlorobenzen or 1,4-dichlorobenzene), Croatica Chemica Acta, 80(1),9-15.
22. [22] Günal, A. (2012). Parafenilendiamin Ligand Molekülünden Elde Edilen Hofmann-tipi Konak-Konuk Bileşiklerinin İnfrared Spektroskopisi ve Termogravimetrik Yöntemler ile İncelenmesi, Yüksek Lisans Tezi, Dumlupınar Üniversitesi, Fen Bilimleri Enstitüsü, Kütahya. 85s.