Structure and stability range of a hexanuclear Th(IV)-glycine complex.

A hexanuclear Th(IV)-glycine complex was observed by Th L(3)-edge EXAFS measurements in an aqueous solution. Within the stability range of this complex the positively charged hexanuclear species Th(6)(μ(3)-O)(4)(μ(3)-OH)(4)(H(2)O)(6)(Gly)(6)(HGly)(6) was preserved in a crystal with the composition [Th(6)(μ(3)-O)(4)(μ(3)-OH)(4)(H(2)O)(6)(Gly)(6)(HGly)(6)]·(NO(3))(3)(ClO(4))(3)(H(2)O)(3). This complex appears as a result of a competing reaction between hydrolysis and ligation by glycine. At a pH value below the stability range of the hexanuclear complex, crystals with the composition [Th(H(2)O)(3)(HGly)(3)]·(ClO(4))(4)H(2)O were obtained from the solution. Three water molecules in the thorium coordination sphere indicate that this complex occurs prior to the onset of Th(IV) hydrolysis.