Altı koordinasyonlu Ni(II) ditiyofosfonato komplekslerinin sentez ve karakterizasyonu

Abstract

İki pertiyofosfonik asit anhidritinin, 2,4-bis(Rx,y)-1,3-ditiya-2,4-difosfetan 2,4- disulfür [(Rx,y-P(S)S)2; Rx= 4-metoksi-2-metilfenil- (SAV-B1) ve Ry= 4-metoksi-3-metilfenil (SAV-B2)] sentezlendi. Bu pertiyofosfonik asit anhidritlerinin etil alkolle reaksiyonundan sentezlenen 2 ditiyofosfonik asit (Rx,y(EtO)P(S)SH)), kararlı amonyum tuzlarına ([NH4][S2P(Rx,y)(OEt)]) dönüştürüldü. Amonyum tuzlarının NiCl2.6H2O tuzuyla reaksiyonundan dört koordinasyonlu iki ditiyofosfonato nikel(II) kompleksi ([Ni(S2P(Rx,y)(OEt))2]) hazırlandı. Daha öceden bilinen dört koordinasyonlu komplekslerin değişik Lewis bazı ligandlarıyla (piridin=py, bipiridin= bipy ve fenantrolin=phen), yeni altı koordinasyonlu kompleksleri ([(phen)3Ni][(S2P(Rx,y)(OEt))2] ve [(L)nNi(S2P(Rx,y)(OEt))2], n=2, L= py ; n=1, bipy) sentezlendi. Yeni komplekslerin elementel analizleri, IR, ESI-MS ve manyetik alınganlık ölçümleriyle (meff) yapıları aydınlatıldı.

Two compounds, 2,4-bis(Rx,y)-1,3-dithia-2,4-diphosphetane 2,4-disulfide ([(Rx,y-P(S)S)2; Rx= 4-methoxy-2-methylphenyl- (SAV-B1) and Ry= 4-methoxy-3-methylphenyl (SAV-B2)]), were produced by synthesising perthiophosphonic acid anhydrides. Two dithiophosphonic acids were synthesised by reacting perthiophosphonic acid anhydrides with ethyl alcohol (Rx,y(EtO)P(S)SH). These dithiophosphonic acids were then transformed into stable ammonium salts ([NH4][S2P(Rx,y)(OEt)]). Two nickel(II) complexes with dithiophosphonato ligands, each coordinated to four atoms to sulfur, were synthesized by reacting ammonium salts with NiCl2.6H2O. The synthesis of new six-coordinated complexes, namely [(phen)3Ni][(S2P(Rx,y)(OEt))2] and [(L)nNi(S2P(Rx,y)(OEt))2], where n=2 and L=py ; n=1 and L=bipy, were carried out using various Lewis base ligands such as pyridine (py), bipyridine (bipy), and phenanthroline (phen). The structures of the novel complexes were determined by elemental analysis, infrared spectroscopy (IR), electrospray ionisation mass spectrometry (ESI-MS), and magnetic susceptibility measurements (meff).