Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry.

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 of 1 - 3 feature 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 (for 1 ) or a NO group (for 2 ) to complete a square-pyramidal geometry. In the nitrosyl complex 2 , the Ir-N-O group has a bent geometry (the angle is 125°). The CV data for 1 and 3 show two reversible waves between 0 and -1.6 V (vs. Ag/AgCl). Reversible oxidation was also found at E1/2 = 0.60 V for 1 . Magnetochemical measurements for 2 in 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 complex 2 is 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 of 2 as a result of its decomposition. The EPR spectrum of 4 in CH2 Cl2 is 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.