Neutral phosphate and phosphate butylesters as ligands

Abstract

Interaction of tri-n-butyl phosphate (TBP), tri-iso-bu-tyl phosphate (TIBP) of di-n-butyl n-butylphosphate DBBP) with hydratd #d metal perchlorates in triethyl orthoformate leads to the formation of crystalline complexes of the general type ML4(CiO4)2.xH2O (x = 1,2). Characterization of these xomplexes by means of spectral, magnetic and conductance studies led to the following tentative formulations: [M(TBP)4 (OH2)(OClO3)](ClO4); [M(TIBP)4(OH2)](ClO4)2; [M (DBBP)4(OH2)2(ClO4)2 (M Mn,CoNi);[Cu(DBBP)4(OH2)2(ClO4)2. According to these assignments, the TIBP complexes and that of Cu11 withDBBP involved pentacoordinated complex cations, while in the other DBBp complexes the cation is hexacoordinated. The cationic TBP complexes are hexacoordinated, probably involving one coordinated monodentate per chlorato group. The factors influencing the stabilization of mono or di-aquo adducts rather than the [Ml4] (ClO4)2 solvates are discussed.