Details

Autor(en) / Beteiligte

• Romashev, Nikolai F
• Bakaev, Ivan V
• Komlyagina, Veronika I
• Abramov, Pavel A
• Mirzaeva, Irina V
• Nadolinny, Vladimir A
• Lavrov, Alexander N
• Kompan'kov, Nikolai B
• Mikhailov, Artem A
• Fomenko, Iakov S
• Novikov, Alexander S
• Sokolov, Maxim N
• Gushchin, Artem L

Titel

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

Ist Teil von

• International journal of molecular sciences, 2023-06, Vol.24 (13), p.10457

Ort / Verlag

Switzerland: MDPI AG

Erscheinungsjahr

2023

Link zum Volltext

Quelle

Elektronische Zeitschriftenbibliothek (Open access)

Beschreibungen/Notizen

• A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] ( ), [Ir(cod)(NO)(dpp-bian)](BF ) ( ) and [Ir(cod)(dpp-bian)](BF ) ( ), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of - 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 ) or a NO group (for ) to complete a square-pyramidal geometry. In the nitrosyl complex , the Ir-N-O group has a bent geometry (the angle is 125°). The CV data for and show two reversible waves between 0 and -1.6 V (vs. Ag/AgCl). Reversible oxidation was also found at E = 0.60 V for . Magnetochemical measurements for in a range from 1.77 to 300 K revealed an increase in the magnetic moment with increasing temperature up to 1.2 μ (at 300 K). Nitrosyl complex is unstable in solution and loses its NO group to yield [Ir(cod)(dpp-bian)](BF ) ( ). A paramagnetic complex, [Ir(cod)(dpp-bian)](BF ) ( ), was also detected in the solution of as a result of its decomposition. The EPR spectrum of in CH Cl is described by the spin Hamiltonian Ĥ = gβHŜ with S = 1/2 and g = g = 2.393 and g = 1.88, which are characteristic of the low-spin 5d -Ir(II) state. DFT calculations were carried out in order to rationalize the experimental results.