Manufacture method for aqueous formulation of manganese-containing coordination complex, formulation, and method of treatment

A method of manufacturing an aqueous formulation of a manganese-containing coordination complex, the aqueous formulation comprising the manganese-containing coordination complex, a chloride anion, and a dianion, the method comprising:

• combining a source of the manganese-containing coordination complex with a source of chloride anion in an aqueous solution;
• and
• simultaneously with or following combination of the source of chloride anion and the source of manganese-containing coordination complex in the aqueous solution, providing a source of a dianion to the aqueous solution to form the aqueous formulation,
• wherein an amount of the source of chloride anion that is combined with the manganese-containing coordination complex is sufficient to provide a concentration of chloride ion in the aqueous formulation that is in excess of a concentration of dianion in the aqueous formulation, and
• wherein the manganese-containing coordination complex comprises a pentaaza macrocyclic ring complex having a structure according to Formula (I)
• wherein
• M is Mn2+ or Mn3+;
• R1, R2, R′2, R3, R4, R5, R′5, R6, R′6, R7, R8, R9, R′9, and R10 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocyclyl, an amino acid side chain moiety, or a moiety selected from the group consisting of —OR11, —NR11R12, —COR11, —CO2R11, —CONR11R12, —SR11, —SOR11, —SO2R11, —SO2NR11R12, —N(OR11)(R12), —P(O)(OR11)(OR12), —P(O)(OR11)(R12), and —OP(O)(OR11)(OR12), wherein R11 and R12 are independently hydrogen or alkyl;
• U, together with the adjacent carbon atoms of the macrocycle, forms a fused substituted or unsubstituted, saturated, partially saturated or unsaturated, cycle or heterocycle having 3 to 20 ring carbon atoms;
• V, together with the adjacent carbon atoms of the macrocycle, forms a fused substituted or unsubstituted, saturated, partially saturated or unsaturated, cycle or heterocycle having 3 to 20 ring carbon atoms;
• W, together with the nitrogen of the macrocycle and the carbon atoms of the macrocycle to which it is attached, forms an aromatic or alicyclic, substituted or unsubstituted, saturated, partially saturated or unsaturated nitrogen-containing fused heterocycle having 2 to 20 ring carbon atoms, provided that when W is a fused aromatic heterocycle the hydrogen attached to the nitrogen which is both part of the heterocycle and the macrocycle and R1 and R10 attached to the carbon atoms which are both part of the heterocycle and the macrocycle are absent;
• X and Y represent suitable ligands which are derived from any monodentate or polydentate coordinating ligand or ligand system or the corresponding anion thereof;
• Z is a counterion;
• n is an integer from 0 to 3;
• and
• the dashed lines represent coordinating bonds between the nitrogen atoms of the macrocycle and the transition metal, manganese.