Cyclic alkyl(amino) carbene stabilized two- and three-coordinate Fe(I) complexes, (cAAC)₂FeCl (2) and [(cAAC)₂Fe][B(C₆F₅)₄] (3), respectively, were prepared and thoroughly studied by a bouquet of analytical techniques as well as theoretical calculations. Magnetic susceptibility and Mössbauer spectroscopy reveal the +1 oxidation state and S = 3/2 spin ground state of iron in both compounds. 2 and 3 show slow magnetic relaxation typical for single molecule magnets under an applied direct current magnetic field. The high-frequency EPR measurements confirm the S = 3/2 ground state with a large, positive zero-field splitting (∼20.4 cm^–1) and reveal easy plane anisotropy for compound 2. CASSCF/CASPT2/RASSI-SO ab initio calculations using the MOLCAS program package support the experimental results.