A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] (1), [Ir(cod)(NO)(dpp-bian)](BF4)2(2) and [Ir(cod)(dpp-bian)](BF4) (3), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of1–3feature a square planar backbone consisting of two C = C π-bonds of 1,5-cyclooctadiene (cod) and two nitrogen atoms of dpp-bian supplemented with a chloride ion (for1) or a NO group (for2) to complete a square-pyramidal geometry. In the nitrosyl complex2, the Ir-N-O group has a bent geometry (the angle is 125°). The CV data for1and3show two reversible waves between 0 and -1.6 V (vs. Ag/AgCl). Reversible oxidation was also found at E1/2= 0.60 V for1. Magnetochemical measurements for2in a range from 1.77 to 300 K revealed an increase in the magnetic moment with increasing temperature up to 1.2 μB(at 300 K). Nitrosyl complex2is unstable in solution and loses its NO group to yield [Ir(cod)(dpp-bian)](BF4) (3). A paramagnetic complex, [Ir(cod)(dpp-bian)](BF4)2(4), was also detected in the solution of2as a result of its decomposition. The EPR spectrum of4in CH2Cl2is described by the spin Hamiltonian Ĥ = gβHŜ with S = 1/2 and gxx= gyy= 2.393 and gzz= 1.88, which are characteristic of the low-spin 5d7-Ir(II) state. DFT calculations were carried out in order to rationalize the experimental results.