Polihedral Oligomerik Silseskioksan (POSS) Bileşiklerinin Schiff Bazları ve Cu(II) ve Ni(II) Komplekslerinin Sentezi ve Karakterizasyonu

Bu çalışmada, 3-aminopropiltrietoksisilan (APTES) ve N-(2-aminoetil)-3-aminopropiltrimetoksisilan (AEPTMS) kullanılarak iki farklı polihedral oligomerik silseskioksan (POSS) sentezlenmiştir. Elde edilen bu POSS bileşikleri, salisilaldehit ve 5-bromosalisilaldehit ile kondenzasyon tepkimesi sonucu POSS Schiff bazları sentezlenmiştir. POSS ve ligand özelliğindeki türevlerinin yapıları spektroskopik (Elementel analiz (C, H, N), 1H-NMR, 29Si NMR, FT-IR) yöntemlerle aydınlatılmıştır. Schiff Bazlarının Cu(II) ve Ni(II) metal kompleksleri sentezlenmiştir. İzole edilen POSS Schiff bazı metal komplekslerinin yapıları FT-IR, Magnetik duyarlılık terazisi ve ICP-OES ile aydınlatılmaya çalışılmıştır. Sonuçlar, metal iyonlarının Schiff bazlarına fenolik oksijen ve azometin azotu üzerinden bağlandığını göstermiştir.

Synthesis and Characterization of Schiff Bases and Cu(II) and Ni(II) Complexes of Polyhedral Oligomeric Silsesquioxane (POSS) Compounds

In this study, two different polyhedral oligomeric silsesquioxane (POSS) were synthesized using 3-aminopropyltriethoxysilane (APTES) and N-(2-aminoethyl)-3- aminopropyltrimethoxysilane (AEPTMS). POSS Schiff bases were synthesized as a result of the condensation reaction of POSS compounds with salicylaldehyde and 5-bromosalicylaldehyde. The structures of POSS and its ligand derivatives were by spectroscopic (Elemental analysis (C, H, N), 1HNMR, 29Si-NMR, FT-IR) methods. Cu(II) and Ni(II) metal complexes of Schiff Bases were also synthesized. The structures of the isolated POSS Schiff base metal complexes were tried to be clarified with FT-IR, Magnetic susceptibility balance and ICP-OES. The results showed that metal ions bind to Schiff bases via phenolic oxygen and azomethine nitrogen.

___

  • Allan JR, Gardner AR, Mccloy B, Smith WE, 1992. Structural and thermal studies of the chlorocomplexes of cobalt, nickel and copper with 2,6- diaminopyridine and an assessment of their suitability as antistatic additives for polyethylene. Thermochimica Acta, 208: 125-131.
  • Arshadi M, Ghiaci M, 2011. Highly efficient solvent free oxidation of ethylbenzene using some recyclable catalysts: The role of linker in competency of manganese nanocatalysts. Applied Catalysis A: General, 399: 75-86.
  • Berber N, Arslan M, 2020. Preparation and characterization of some Schiff base compounds. Adıyaman University Journal of Science, 10(1):179-188.
  • Durak D, Delikanlı A, Demetgül C, Kani İ, Serin S, 2013. Crystal structure of an unsymmetrical Schiff base, immobilization of its cobalt and manganese complexes on a silica support, and catalytic studies. Transition Metal Chemistry, 38:199–206.
  • Gravel MC, Zhang C, Dinderman M, Laine RM, 1999. Octa(3-chloroammoniumpropyl) octasilsesquioxane. Applied Organometallic Chemistry 13: 329–336.
  • Grigoropoulou G, Stathi P, Karakassides MA, Louloudi M, Deligiannakis Y, 2008. Functionalized SiO2 with N-, S-containing ligands for Pb(II) and Cd(II) adsorption, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 320(1–3): 25-35.
  • Gündüz T, 1994. Koordinasyon Kimyası, Ankara Üniversitesi Fen Fakültesi Kimya Bölümü, Ankara.
  • Harrison PG, 1997. Silicate cages:precursors to new materials. Journal of Organometallic Chemsitry, 542:141.
  • Hill A, Fink MJ, 2008. Advances in Organometallic Chemistry. Academic Press, Volume 57, pp 50-52, USA.
  • İspir E. 2014. Synthesis and characterization of silica-supported Schiff base ligands and their metal complexes: applications as catalysts for the oxidation of alkanes. Phosphorus, Sulfur, and Silicon, 189:1644–1655.
  • Lichtenhan JD, Schwab JJ, Feher FJ, Soulivong D, 1999. U.S. Patent 5942638.
  • Mehta A, Tembe G, Białek M, Parikh P, Mehta G, 2012. Synthesis and catalytic studies of Ti-anchored disilanol isobutyl-POSS/alkylaluminum system. Journal of Molecular Catalysis A: Chemical, 361-362: 17-28.
  • Scovill JP, 1982. 2-Acetylpyridine thiosemicarbazones 3. Complexes with transition metals as antimalarial and antileukemic agents, Journal of Medicinal Chemistry, 25(10): 1261-1264.
  • Serin S, 1980. 1,3-Difenil-2-tio-4,5-bis(hidroksiimino)-1,2,4,5-tetrahidroimidazol eldesi, geometrik izomerleri, geçiş metalleri ile kompleks formasyonları. K.T.Ü. Fen Bilimleri Enstitüsü, Doktora Tezi, Trabzon (Basılmış).
  • Tarafder MTH, Mial LMA, 1986. Novel peroxo complexes of zirconium containing organicligants, Inorganic Chemistry, 25(13): 2265-2268.
  • Timur M, Demetgül C, 2017. Synthesis and metal ıon uptake studies of silica gel -ımmobilized schiff base derivatives and catalytic behaviors of their Cu(II) complexes. Iranian Journal of Chemistry and Chemical Engineering, 36(4): 111-122.
  • Tingaut P, Hauert R, Zimmermann T, 2011. Highly efficient and straightforward functionalization of cellulose films with thiol-ene click chemistry. Journal of Materials Chemistry, 2011(21): 16066–16076.
  • Tümer M, Köksal H, Serin S. Patat Ş, 1997. Synthesis and characterization of some cobalt(II), nickel(II) and zinc(II) complexes with Schiff bases derived from the reaction of 4-hydroxisalicylaldehyde and o-vanillin with 3,5-di(tert-butyl)-4-hydroxyaniline. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 27(1): 59-68.
  • Wheeler PA, Fu BX, Lichtenhan JD, Weitao J, Mathias LJ, 2006. Incorporation of metallic POSS, POSS copolymers, and new functionalized poss compounds into commercial dental resins. Journal of Applied Polymer Science, 102: 2856–2862.
  • Xie K, Yanli Z, Si C, 2010. Synthesis and characterization of reactive polyhedral oligomeric silsesquioxanes (R-POSS) containing multi-N-methylol groups. Journal of Organometallic Chemistry. 695(5): 687-691.