In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.

Titanium complexes containing catecholate ligands can be desirable active materials for flow batteries and other electrochemical energy storage systems. Such complexes can be formed, potentially on very large scales, through reacting a catechol compound in an organic solvent with titanium tetrachloride, and then obtaining an aqueous phase containing an alkali metal salt form of the titanium catechol complex. More specifically, the methods can include: forming a catechol solution and heating, adding titanium tetrachloride to the catechol solution, reacting the titanium tetrachloride with a catechol compound to evolve HCl gas and to form an intermediate titanium catechol complex, and adding an alkaline aqueous solution to the intermediate titanium catechol complex to form an alkali metal salt form titanium catechol complex that is at least partially dissolved in an aqueous phase. The aqueous phase can be separated from an organic phase. The resulting complexes can be substantially free of alkali metal halide salts.

Titanium complexes containing catecholate ligands can be desirable active materials for flow batteries and other electrochemical energy storage systems. Such complexes can be formed, potentially on very large scales, through reacting a catechol compound in an organic solvent with titanium tetrachloride, and then obtaining an aqueous phase containing an alkali metal salt form of the titanium catechol complex. More specifically, the methods can include: forming a catechol solution and heating, adding titanium tetrachloride to the catechol solution, reacting the titanium tetrachloride with a catechol compound to evolve HCl gas and to form an intermediate titanium catechol complex, and adding an alkaline aqueous solution to the intermediate titanium catechol complex to form an alkali metal salt form titanium catechol complex that is at least partially dissolved in an aqueous phase. The aqueous phase can be separated from an organic phase. The resulting complexes can be substantially free of alkali metal halide salts.

A method for the manufacture of a metal salt of a hydroxy-substituted aromatic compound comprises: contacting a hydroxy-substituted aromatic compound with a base comprising a metal cation in molten diphenyl sulfone or sulfolane to provide a mixture comprising water, diphenyl sulfone or sulfolane, and a metal salt of the hydroxy-substituted aromatic compound; and removing water from the mixture in the absence of an azeotrope solvent to provide the metal salt of the hydroxy-substituted aromatic compound that contains less than 3,000 ppm of water.

A method for the manufacture of a metal salt of a hydroxy-substituted aromatic compound comprises: contacting a hydroxy-substituted aromatic compound with a base comprising a metal cation in molten diphenyl sulfone or sulfolane to provide a mixture comprising water, diphenyl sulfone or sulfolane, and a metal salt of the hydroxy-substituted aromatic compound; and removing water from the mixture in the absence of an azeotrope solvent to provide the metal salt of the hydroxy-substituted aromatic compound that contains less than 3,000 ppm of water.

Coordination complexes can have a metal center with at least one unsubstituted catecholate ligand and at least one monosulfonated catecholate ligand or a salt thereof bound thereto. Some coordination complexes can have a formula of D.sub.gTi(L.sub.1).sub.x(L.sub.2).sub.y, in which D is a counterion selected from NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+, or any combination thereof; g ranges between 2 and 6; L.sub.1 is an unsubstituted catecholate ligand; L.sub.2 is a monosulfonated catecholate ligand; and x and y are non-zero numbers such that x+y=3. Methods for synthesizing such coordination complexes can include providing a neat mixture of catechol and a sub-stoichiometric amount of sulfuric acid, heating the neat mixture to form a reaction product containing catechol and a monosulfonated catechol or a salt thereof, and forming a coordination complex from the reaction product without separating the catechol and the monosulfonated catechol or the salt thereof from one another.

Coordination complexes can have a metal center with at least one unsubstituted catecholate ligand and at least one monosulfonated catecholate ligand or a salt thereof bound thereto. Some coordination complexes can have a formula of D.sub.gTi(L.sub.1).sub.x(L.sub.2).sub.y, in which D is a counterion selected from NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+, or any combination thereof; g ranges between 2 and 6; L.sub.1 is an unsubstituted catecholate ligand; L.sub.2 is a monosulfonated catecholate ligand; and x and y are non-zero numbers such that x+y=3. Methods for synthesizing such coordination complexes can include providing a neat mixture of catechol and a sub-stoichiometric amount of sulfuric acid, heating the neat mixture to form a reaction product containing catechol and a monosulfonated catechol or a salt thereof, and forming a coordination complex from the reaction product without separating the catechol and the monosulfonated catechol or the salt thereof from one another.

A method for the manufacture of a metal salt of a hydroxy-substituted aromatic compound comprises: contacting a hydroxy-substituted aromatic compound with a base comprising a metal cation in molten diphenyl sulfone or sulfolane to provide a mixture comprising water, diphenyl sulfone or sulfolane, and a metal salt of the hydroxy-substituted aromatic compound; and removing water from the mixture in the absence of an azeotrope solvent to provide the metal salt of the hydroxy-substituted aromatic compound that contains less than 3,000 ppm of water.

A method for the manufacture of a metal salt of a hydroxy-substituted aromatic compound comprises: contacting a hydroxy-substituted aromatic compound with a base comprising a metal cation in molten diphenyl sulfone or sulfolane to provide a mixture comprising water, diphenyl sulfone or sulfolane, and a metal salt of the hydroxy-substituted aromatic compound; and removing water from the mixture in the absence of an azeotrope solvent to provide the metal salt of the hydroxy-substituted aromatic compound that contains less than 3,000 ppm of water.

A method for the manufacture of a metal salt of a hydroxy-substituted aromatic compound comprises reacting a hydroxy-substituted aromatic compound with a base comprising a metal cation in an aqueous medium to provide a mixture comprising water and a metal salt of the hydroxy-substituted aromatic compound; contacting the mixture with a substantially water-immiscible solvent at a temperature greater than the boiling point of water at a prevailing pressure; introducing an optionally substituted C1-6 aliphatic alcohol; and removing water and the alcohol to provide a slurry comprising the metal salt of the hydroxy-substituted aromatic compound and the water-immiscible solvent.