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Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry.
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.
Affiliation
  • Romashev NF; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Bakaev IV; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Komlyagina VI; Department of Natural Sciences, Novosibirsk State University, Novosibirsk 630090, Russia.
  • Abramov PA; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Mirzaeva IV; Department of Natural Sciences, Novosibirsk State University, Novosibirsk 630090, Russia.
  • Nadolinny VA; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Lavrov AN; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk 634034, Russia.
  • Kompan'kov NB; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Mikhailov AA; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Fomenko IS; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Novikov AS; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
  • Sokolov MN; Laboratoire de Cristallographie, Résonance Magnétique et Modélisations, Université de Lorraine, CNRS, CRM2, UMR 7036, 54000 Nancy, France.
  • Gushchin AL; Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
Int J Mol Sci ; 24(13)2023 Jun 21.
Article in En | MEDLINE | ID: mdl-37445638
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 CH2Cl2 is described by the spin Hamiltonian H = gßHS 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.
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Full text: 1 Collection: 01-internacional Database: MEDLINE Main subject: Iridium Language: En Journal: Int J Mol Sci Year: 2023 Document type: Article Affiliation country: Country of publication:

Full text: 1 Collection: 01-internacional Database: MEDLINE Main subject: Iridium Language: En Journal: Int J Mol Sci Year: 2023 Document type: Article Affiliation country: Country of publication: