Fenantrolin İçerikli Organoditiyo-Fosfor Grubu Nikel Komplekslerinin Sentezi Ve Yapilarinin Aydinlatilmasi

Abstract

ÖZETBu tezde, literatürde daha önceden sentezlenmiş 7 ditiyofosfonik asit ((p-MeO-C6H4)PS(SH)(OR)= DTPOAn, (n= 1-7); R= 3-pentyl-, DTPOA1; R= 1-fenil-1 propil-, DTPOA2; R= 4-tert-bütil benzil-, DTPOA3; R= difenilmetil-, DTPOA4; R= 4-tert-bütil siklohekzil-, DTPOA5; R= 3 fenil-1-propil-, DTPOA6; R= 3-metil-1-bütil-, DTPOA7) ve 4 ditiyofosfinik asit ((p-MeO-C6H4)PS(SH)(R)= DTPAn n= 8-10; R= 3-metil-1-bütil-, DTPA8; R= 2-metilpropil-, DTPA9; R= 1-metilpropil-, DTPA10) sentezlendi. DTPOA'ler Lawesson reaktifinin (LR, 2,4-bis(4-metoksifenil)-1,3,2,4-ditiadifosfetan-2,4-disülfür) alkollerle reaksiyonundan elde edilirken, DTPA'ler ise LR'nin Grignard bileşiklerinin reaksiyonundan elde edildi. Ham DTPOA ve DTPA'ler amonyak gazıyla amonyum tuzlarına dönüştürüldüler ([NH4][DTPOAn] ve [NH4][DTPAn]). Bu tuzların Ni(II) iyonuyla reaksiyonundan daha önceden sentezlenmiş dört koordinasyonlu 10 adet [Ni(DTPOAn)2] ve [Ni(DTPAn)2] kompleksleri sentezlendi. Bu komplekslerin 1,10-fenantrolinle reaksiyonundan 7 yeni fenantrolin nikel ditiyofosfonik asit kompleksi ([Ni(Phen)3][(DTPOAn)2]) ve 3 yeni fenantrolin nikel ditiyofosfinik asit kompleksi ([Ni(Phen)3][(DTPAn)2]) olmak üzere toplamda 10 yeni kompleks sentezlenmiştir.Bileşiklerin yapıları element analizi, kütle spektrometresi (ESI+ ve ESI-), FT-IR, Raman, spektroskopisiyle ve manyetik duyarlılık ölçümleriyle açıklanmıştır.Anahtar Kelimeler: Fenantrolin, Fenantrolin Ditiyofosfonat kompleksleri, Fenantrolin Ditiyofosfinat kompleksleri, Lawesson Reaktifi.Bu tez, Yozgat Bozok Üniversitesi Proje Koordinasyon Uygulama ve Araştırma Merkezi (BAP) tarafından 6602c-FEN/19-271 nolu projesiyle desteklenmiştir.

ABSTRACTIn this thesis, 7 dithiophosphonic acid ((p-MeO-C6H4)PS(SH)(OR)= DTPOAn, (n= 1-7); R= 3-pentyl-, DTPOA1; R= 1-phenyl-1-propyl-, DTPOA2; R= tert-butyl benzyl -, DTPOA3; R= diphenylmethyl-, DTPOA4; R= 4-tert-butylcyclohexyl-, DTPOA5; R= 3 phenyl-1-propyl-, DTPOA6; R= 3-methyl-1-butyl-, DTPOA7) and 3 dithiophosphinic acid ((p-MeO-C6H4)PS(SH)(R)= DTPAn n= 8-10; R= 3-methyl-1-bütyl-, DTPA8; R= 2-methylpropyl-, DTPA9; R= 1-methyl propyl-, DTPA10) which were obtained previously in the literature were synthesized. DTPOAs were obtained from the reaction of Lawesson reagent (LR, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide) with alcohols, while DTPAs were obtained from the addition reaction of LR with Grignard compounds. Crude DTPOAs and DTPAs were converted to ammonium salts with ammonia gas ([NH4][DTPOAn] and [NH4][DTPAn]). The dithiophosphonato Ni(II) and dithiophosphinato Ni(II) complexes which are four coordinated were prepared by the reaction of Ni(II) ion and ammonium salts ([Ni(DTPOAn)2] and [Ni(DTPAn)2]). A total of 10 new complexes were obtained from by the reaction of [Ni(DTPOAn)2], [Ni(DTPAn)2 and 1,10-phenantroline including 7 new phenatroline nickel dithiophosphonic acids ([Ni(Phen)3][(DTPOAn)2]) and 3 new phenatroline nickel dithiophosphinic acids ([Ni(Phen)3][(DTPAn)2]).The characterization of the complexes were done by elemental analysis, mass spectrometry (ESI + and ESI-), FT-IR, Raman spectroscopy and magnetic susceptibility measurements. Key Words : Phenantroline, Phenantroline Dithiophosphonate Complexes, Phenantroline Dithiophosphinate Complexes, Lawesson's Reagent.This thesis is supported by the Project Coordination Application and Research Center of Bozok University [BAP 6602c-FEN/19-271].