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.