Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry
| Parent link: | International Journal of Molecular Sciences.— .— Basel: MDPI AG Vol. 24, iss. 13.— 2023.— Article number 10457, 21 p. |
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| Drugi avtorji: | , , , , |
| Izvleček: | Title screen 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 Текстовый файл |
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2023
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| Online dostop: | https://doi.org/10.3390/ijms241310457 |
| Format: | Elektronski Book Chapter |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=682091 |
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| 200 | 1 | |a Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry |f Nikolai F. Romashev, Ivan V. Bakaev, Veronika I. Komlyagina [et al.] | |
| 203 | |a Текст |b визуальный |c электронный | ||
| 283 | |a online_resource |2 RDAcarrier | ||
| 300 | |a Title screen | ||
| 320 | |a References: 109 tit | ||
| 330 | |a 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 | ||
| 336 | |a Текстовый файл | ||
| 461 | 1 | |t International Journal of Molecular Sciences |c Basel |n MDPI AG | |
| 463 | 1 | |t Vol. 24, iss. 13 |v Article number 10457, 21 p. |d 2023 | |
| 610 | 1 | |a электронный ресурс | |
| 610 | 1 | |a труды учёных ТПУ | |
| 610 | 1 | |a iridium | |
| 610 | 1 | |a BIAN | |
| 610 | 1 | |a iridium(II) | |
| 610 | 1 | |a nitrosyl complexes | |
| 610 | 1 | |a synthesis | |
| 610 | 1 | |a cyclic voltammetry | |
| 610 | 1 | |a redox-active ligands | |
| 610 | 1 | |a non-innocence | |
| 610 | 1 | |a crystal structure; EPR spectroscopy | |
| 610 | 1 | |a static magnetic susceptibility | |
| 610 | 1 | |a redox isomerism | |
| 610 | 1 | |a DFT calculations | |
| 701 | 1 | |a Romashev |b N. F. |g Nikolai | |
| 701 | 1 | |a Bakaev |b I. V. |g Ivan | |
| 701 | 1 | |a Komlyagina |b V. I. |g Veronika | |
| 701 | 1 | |a Abramov |b P. A. |c chemist |c professor, senior researcher at Tomsk Polytechnic University, Doctor of Chemical Sciences |f 1985- |g Pavel Aleksandrovich |9 88582 | |
| 701 | 1 | |a Mirzaeva |b I. V. |g Irina | |
| 801 | 0 | |a RU |b 63413507 |c 20251003 | |
| 850 | |a 63413507 | ||
| 856 | 4 | |u https://doi.org/10.3390/ijms241310457 |z https://doi.org/10.3390/ijms241310457 | |
| 942 | |c CF | ||