The structural investigation is reported of the reactions between components utilized in photothermographic imaging systems, including toners, developers and silver with potential ligands such as triphenylphosphine, tribromomethylsulfonylbenzothiazole and 2-mercapto-benzimidazole. Depending on the complexing agent and silver counterion, various forms of silver complexes can be isolated and characterized. This report demonstrates the interactions, and characterizes the new compounds formed between various components in the photothermographic materials with emphasis on the ormulation containing silver carboxylate, the toner system comprising phthalazine and phthalic acid and phenolic type developers.