Complexes of diisopropyl methylphosphonate with metal salts containing complexing anionic groups

Abstract

Although the synthesis of complexes of diisopropyl methylphosphonate (DIMP) with metal salts containing anions with coordinating ability presents severe difficulties in most cases, a number of complexes have been isolated and characterized by means of spectral, magnetic and conductance studies. These include nitrato and thiocyanato complexes of the types [UO 2(DIMP) 2(O 2NO) 2] and [M(DIMP) 4(NCS) 2](M = Mg, Ni), and quaternary crystalline complexes obtained from systems of the type MgCl 2-MCl 2-DIMP-H 2O (M = Mn, Co, Ni, Cu, Zn). No stable or sufficiently pure complexes of DIMP with 3 d or alkaline earth metal halides could be obtained. By utilization of equimolar amounts of anhydrous MgCl 2 and MCl 2 hydrate in the presence of DIMP, chloride ions are transferred from Mg(II) to M(II) and the chlorometallate anion is stabilized by the large complex cation which consists of Mg(II) coordinated to DIMP and water molecules and, in some cases, chloride ions. The complexes synthesized in this way were assigned the structures [Mg(DIMP) 4(H 2O) 2] [MCl 4](M = Mn, Co, Zn), [MgCl(DIMP) 3(H 2O) 2][NiCl 3(DIMP)] and [MgCl(DIMP)(H 2O) 4][CuCl 3]. DIMP. The latter complex is one of the few examples of a stable compound of the trichlorocuprate (II) anion. The structure of this compound involves one free DIMP molecule enclosed in cavities in the lattice.