Research output: Contribution to journal › Article › peer-review
Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry. / Romashev, Nikolai F; Bakaev, Ivan V; Komlyagina, Veronika I et al.
In: International Journal of Molecular Sciences, Vol. 24, No. 13, 10457, 21.06.2023.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry
AU - Romashev, Nikolai F
AU - Bakaev, Ivan V
AU - Komlyagina, Veronika I
AU - Abramov, Pavel A
AU - Mirzaeva, Irina V
AU - Nadolinny, Vladimir A
AU - Lavrov, Alexander N
AU - Kompan'kov, Nikolai B
AU - Mikhailov, Artem A
AU - Fomenko, Iakov S
AU - Novikov, Alexander S
AU - Sokolov, Maxim N
AU - Gushchin, Artem L
N1 - Funding: Financial support from the Russian Science Foundation (grant 21-13-00092) is acknowledged.
PY - 2023/6/21
Y1 - 2023/6/21
N2 - 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 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.
AB - 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 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.
KW - Iridium/chemistry
KW - Ligands
KW - Crystallography, X-Ray
KW - Oxidation-Reduction
KW - Spectrum Analysis
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85164843708&origin=inward&txGid=33606040b4427e7f3c0bc743f9e24404
UR - https://www.mendeley.com/catalogue/67022269-ad57-3518-af3f-dd955af71e61/
U2 - 10.3390/ijms241310457
DO - 10.3390/ijms241310457
M3 - Article
C2 - 37445638
VL - 24
JO - International Journal of Molecular Sciences
JF - International Journal of Molecular Sciences
SN - 1661-6596
IS - 13
M1 - 10457
ER -
ID: 52794299