THE INVESTIGATION OF HOFMANN TYPE COMPLEXES OF M(O-AMINOTHIOPHENOL)NI(CN)4 (M = CD AND HG) BY FT-IR SPECTROSCOPY

Yıl 2016, Sayı: 037, 47 - 56, 30.12.2017

Zeki Kartal Abdulkerim Yavuz

Öz

In this study, Hofmann Type complexes of o-Aminothiophenol–tetracyanonickel, given by the general formula M(o-Aminothiophenol)Ni(CN)₄ (M = Cd and Hg),
is obtained for the first time through chemical methods. The FT-IR
spectroscopic data in the region of (4000–400) cm^-1 was recorded and the IR
frequencies were given and explained in detail. The spectral analyses, results
of the newly synthesized complex of o–Aminothiophenol tetracyanonickel suggest that these complexes
are new examples of the Hofmann–type complex. In our study, the Hofmann-type complex formed by bounding
electrons of sulfur and nitrogen atoms of o–Aminothiophenol (2ATP) ligand molecule to transition
metal atoms consist of the corrugated |M–Ni(CN)₄|_∞ polymeric
layers which are held in parallel through the chain of (–M–2ATP–M–).

Anahtar Kelimeler

Molecular Spectroscopy, Infrared Spectroscopy, Hofmann-type Complexes, o-Aminothiophenol (2ATP)

HOFMANN TİPİ M(O-AMİNOTİYOFENOL)Nİ(CN)4 (M = CD VE HG) KOMPLEKSLERİNİN FT-IR SPEKTROSKOPİSİ İLE İNCELENMESİ

Öz

Bu
çalışmada, genel formülü M(o-Aminotiyofenol)Ni(CN)₄
(M = Cd ve Hg) olan Hofmann-tipi kompleksler kimyasal yollardan ilk kez elde
edildi.  Elde edilen komplekslerin
infrared spektrumları (4000–400) cm^-1 spektroskopik bölgesinde
alınarak soğurma titreşim modları belirlendi ve onların tanımlamaları yapıldı.
Bu sonuçlar literatürde yer alan diğer Hofmann-tipi komplekslerle
karşılaştırıldı ve benzer sonuçlar gözlendi. Bu çalışmamızdaki Hofmann tipi komplekslerin
o-Aminotiyofenol (2ATP) ligand
molekülünün kükürt ve azot atomları üzerinden geçiş metali atomlarına
bağlanmasıyla oluştuğu ve |M–Ni(CN)₄|_¥  polimerik tabakalarının ise (–M–2ATP–M–)
zincirleri tarafından paralel halde tutulduğu düşünülmektedir.  Bu çalışma sonucunda Hofmann-tipi komplekslere
iki yeni örnek kazandırılmıştır.

Anahtar Kelimeler

Moleküler Spektroskopi, İnfrared Spektroskopisi, Hofmann-Tipi kompleksler, o-Aminotiyofenol (2ATP)

Kaynakça

• [1] Acheampong, M.A. Meulepas, R.J.W. Lens, P.N.L.“Removal of heavy metals and cyanide from gold mine wastewater” J. Chem. Tech. Biotechnol. 85(5), 590-613 (2010).
• [2] Zagury, G.J. Oudjehani, K. Desche ̂nes, L. “Characterization and availability of cyanide in solid mine tailings from gold extraction plants”, Sci. Total Environ. 320, 211-224 (2004).
• [3] Yngard, R.A. Sharma, V.K. Filip, J. Zboril, R. “Ferrate(VI) oxidation of weak-acid dissociable cyanides” Environ. Sci. Technol. 42, 3005-3010 (2008).
• [4] Shirzad Siboni, M. Samarghandi, M.R. Yang, L.K. Lee, S.M. “Photocatalytic removal of cyanide with illuminated TiO2”, Water Sci. Technol. 64, 1383-1387 (2011).
• [5] Lito, P.F. Aniceto, J.P.S. Silva, C.M. “Removal of anionic pollutants from waters and wastewaters and materials perspective for their selective sorption”, Water Air Soil Pollut. 223, 6133-6155 (2012).
• [6] Smolinski, A. Stanczyk, K. Kapusta, K. Howaniec, N. “Chemometric study of the ex situ underground coal gasification wastewater experimental data”, Water Air Soil Pollut. 223, 5745-5758 (2012).
• [7] Pal, P. Kumar, R. “Treatment of Coke Wastewater: A Critical Review for Developing Sustainable Management Strategies”, Separation & Purification Reviews 43(2), 89-123 (2014).
• [8] Kürkçüoğlu, G.S. Yeşilel, O.Z. Çaylı, I. Büyükgüngör, O. ”One- and Two-Dimensional Cadmium(II) Tetracyanonickelate(II) Coordination Polymers With Imidazole and 2-Methylimidazole Ligands”, Journal of Inorganic and Organometallic Polymers and Materials 21(2), 306-315 (2011).
• [9] Hosoya, K. Sekiya, R. Nishikiori, S.I. “A Hofmann pyridine complex: poly[tetra-μ-cyano-di¬pyridine-manganese(II)nickel(II)]”, Acta Cyrstallographica Section E62, 1627-1629 (2006).
• [10] Çetinkaya, F. Kurkcuoğlu, G.S. Yeşilel O.Z. Buyukgungor, O. “Two dimensional heteropolynuclear Zn(II) and Cd(II)-tetracyanopalladate(II) complexes with the 1-ethylimidazole ligand exhibiting C–H⋯Pd interactions”, Polyhedron 55, 10-17 (2013).
• [11] Çetinkaya, F. Kurkcuoğlu, G.S. Yeşilel O.Z. Hokelek, T. “One-dimensional cyano-bridged heterometallic (Cu/Ni and Cu/Pd) complexes with 1-ethylimidazole”, Polyhedron 47, 126-133 (2012).
• [12] Gör, K. Kurkcuoğlu, G.S. Yeşilel O.Z. Buyukgungor, O. “Syntheses, crystal structures and spectroscopic properties of cyano-bridged two-dimensional coordination polymers with 3-methylpyridazine”, Inorg. Chim. Acta 414, 15-20 (2014).
• [13] Kurkcuoğlu, G.S. Karaağac, D. Yeşilel, O.Z Taş, M. “Synthesis, Spectroscopic and Structural Properties of Heteropolynuclear Cyano-Bridged Complexes”Journal of Inorganic and Organometallic Polymers and Materials 22(2), 324-331 (2012).
• [14] Iwamoto, T. Atwood, J.L. Davies, J.E.D. MacNicol, D.D. "Inclusion Compounds", Academic Press, vol. I, Chapter 2, London, 29 (1984).
• [15] İnternet: Online. https://en.wikipedia.org/wiki/2-Aminothiophenol (2016).
• [16] Türk, T. ve Kartal, Z. " M(1,6-Hexanedithiol)Ni(CN)4 bileşiklerinin Kırmızıaltı Spektroskopisi ile İncelenmesi (M = Ni, Cd, Co, Mn ve Zn)", SDU Journal of Science (E-Journal), 9(2), 160 – 169, (2014)
• [17] Griffith, W.P. and Koh, T.Y." Vibrational spectra of 1,2-benzenedithioi, 2-aminothiophenol and 2-aminophenol and their SER spectra", Spectrochimica Acta , Vol. 51A, No. 2, pp. 253-267, (1995).
• [18] Parlak, C. "1 – Fenilpiperazin Molekülünün Titreşim Bandlarının Kuantum Kimyasal Hesaplamalarla Belirlenmesi ve Bu Moleküle Ait Hofmann Tipi Kompleks ve Klatratların Titreşim Spektroskopisiyle İncelenmesi", Doktora Tezi, Anadolu Üniversitesi Fen Bilimleri Enstitüsü, Fizik Anabilim Dalı, 140 (2009).
• [19] McCullough, R.L. Jones, L.H. Crosby, G.A. "An analysis of the vibrational spectrum of the tetracyanonickelate(II) ion in a crystal lattice", Spectrochimica Acta 16 (8), 929-944 (1960).
• [20] Kartal, Z. Sayın, E. "FTIR spectroscopic and thermal study of M(Cyclohexanethiol)2Ni(CN)4·(1,4-dioxane) clathrate (M = Mn, Co, Ni and Cd)", Journal of Molecular Structure 994 (1-3), 170-178 (2011).
• [21] Kartal, Z. "Synthesis, spectroscopic, thermal and structural properties of [M(3-aminopyridine)2Ni(µ-CN)2(CN)2]n (M(II) = Co and Cu)] heteropolynuclear cyano-bridged complexes", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 152 (2016), 577–583 (2015).
• [22] Kartal, Z. "FT-IR spectroscopic and thermal study of M(1,6-hexanedithiol)Ni(CN)4.2(1,4-dioxane) clathrate (M = Mn, Co, Ni and Cd)", Journal of Molecular Structure 1014 (2012), 74–80 (2012).
• [23] Kartal, Z. "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 (2009) 70–75 (2009).
• [24] Bellamy, L.J. Branch, R.F. "The infra-red spectra of chelate compounds. Part II. Metal chelate compounds of β-diketones and of salicylaldehyde", Journal of the Chemical Society (Resumed), (0): 4491-4494 (1954).
• [25] Davies, M. "Infrared Spectroscopy and Molecular Structure", Elsevier, Amsterdam, (1963).
• [26] Nakamoto, K. "Infrared Spectra of Inorganic and Coordination Compounds", 2nd Edition, Wiley-Interscience, New York, (1970).