The spin transitions in two new cationic complexes of iron, i. e., iron bipyridine formate, [Fe/bipy/3]/HCOO/2. 5/HCOOH/ and iron bipyridine tetrafluoro borate, [Fe/bipy/3]/BF4/2. 2H2O have been studied by using Mössbauer spectroscopy. From quadrupole splitting values, at different temperatures, it has been established that both the complexes show the coexistence of both the high spin state and the low spin state at 300 K while complete transformation to low spin state occurs at 77 K. Both compounds were prepared by electrochemical technique. © 1990 Akadémiai Kiadó.