Phosphato complexes of cobalt(III). I. General structural and hydrolytic properties

Abstract

Phosphorus-32 tracer experiments have demonstrated that the phosphato ligand in [Co en₂PO₄]⁰ [Co(NH₃)₄PO₄]^O, [CO(NH₃)₄OH₂HPO₄]⁺, and [Co en₂OH₂.HPO₄]⁺ undergoes slow substitution in acid and alkaline media at 40-60º and that a reversible hydrolysis equilibrium is established from pH 3 to 11. Outside this pH range, acid and base hydrolysis of all these phosphato complexes to diaquo or dihydroxo complexes is complete. The infrared spectra of [Co en₂PO₄]⁰ and [Co(NH₃)₄PO₄]⁰ are consistent with a bidentate phosphato structure and with a monodentate phosphato ligand in CO(NH₃)₅PO₄ and probably [Co(NH₃)₄OH₂HPO₄]⁺I-. The bidentate and monodentate complexes may be rapidly and reversibly interconverted but significant concentrations of the bidentate complexes only persist in the range pH 5.5-7.5. P.m.r, studies have established the predominantly cis configuration of the aquophosphato complexes. These complexes exhibit four acidity constants, one due to the aquo ligand, and three due to the monodentate phosphato ligand. The bidentate [Co en2PO4]⁰ exhibits a single acidity constant above pH 2. The aquophosphato complexes undergo both acid and base hydrolysis entirely by Co-O bond rupture. Acid hydrolysis of [Co en₂PO₄]⁰ also proceeds entirely by Co-O bond rupture but at pH 6.8 and in 0.25M NaOH hydrolysis proceeds by 60-65% Co-O bond rupture and by 30-35% P-O bond rupture.