A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour

Romashev, Nikolai F.; Gushchin, Artem L.; Fomenko, Iakov S.; Abramov, Pavel A.; Mirzaeva, Irina V.; Kompankov, Nikolay B.; Kal’nyi, D. B.; Sokolov, Maxim N.

doi:10.1016/j.poly.2019.114110

Cited by 21 publications

(30 citation statements)

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“…Bis(arylimino)acenaphthenes (BIANs) are redox-active, sterically bulky ligands, widely used as N,N-bidentate ligands in coordination chemistry and catalysis [ 23 , 24 ]. The key feature of BIANs as strong π-acceptor molecules is their ability to accept up to four electrons, which can be reversibly exchanged with the coordinated metal-triggering redox-based chemical processes [ 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ]. Many complexes of late transition metals with BIANs have been reported [ 36 , 37 , 38 , 39 , 40 , 41 ].…”

Section: Introductionmentioning

confidence: 99%

Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry

et al. 2022

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Self-assembly of (Bu4N)4[β-Mo8O26], AgNO3, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu4N)2[β-{Ag(dpp-bian)}2Mo8O26] (1) complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag+ in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding. Quantum chemical calculations were performed to qualify the nature of the Ag-N/Ag-O interactions and to assign the electronic transitions observed in the UV–Vis absorption spectra. The electrochemical behavior of the complex combines POM and redox ligand signatures. Complex 1 demonstrates catalytic activity in the electrochemical reduction of CO2.

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Section: Introductionmentioning

confidence: 99%

Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry

et al. 2022

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“…62 On the contrary, the electrochemical behavior of uncoordinated dpp-Bian was characterized by the irreversible reduction wave at −1.51 V (relative to Ag/AgCl). 63 This behavior is typical of metal complexes with the Biantype ligands, which is a consequence of the pronounced πacceptor properties of the Bian ligand and location of the LUMO orbital on the diimine part (Figure 4). Previously, a Bian-centered reduction for structurally similar complexes has been proven by EPR spectroscopy.…”

Section: ■ Results and Discussionmentioning

confidence: 62%

“…The first redox process appeared at approximately −0.4 V (relative to Ag/AgCl), whereas the second process occurred at about −1.4 V. The reduction process was centered on the dpp-Bian ligand with the formation of the dpp-Bian –/• monoanion and the dpp-Bian 2– dianion (see scheme in Figure ). On the contrary, the electrochemical behavior of uncoordinated dpp-Bian was characterized by the irreversible reduction wave at −1.51 V (relative to Ag/AgCl) …”

Section: Resultsmentioning

confidence: 99%

Heteroleptic Pd(II) and Pt(II) Complexes with Redox-Active Ligands: Synthesis, Structure, and Multimodal Anticancer Mechanism

et al. 2022

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A series of heteroleptic square-planar Pt and Pd complexes with bis(diisopropylphenyl) iminoacenaphtene (dpp-Bian) and Cl, 1,3-dithia-2-thione-4,5-dithiolate (dmit), or 1,3-dithia-2-thione-4,5-diselenolate (dsit) ligands have been prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis, and cyclic voltammetry (CV). The intermolecular noncovalent interactions in the crystal structures were assessed by density functional theory (DFT) calculations. The anticancer activity of Pd complexes in breast cancer cell lines was limited by their solubility. Pd(dpp-Bian) complexes with dmit and dsit ligands as well as an uncoordinated dpp-Bian ligand were devoid of cytotoxicity, while the [Pd(dpp-Bian)Cl2] complex was cytotoxic. On the contrary, all Pt(dpp-Bian) complexes demonstrated anticancer activity in a low micromolar concentration range, which was 8–20 times higher than the activity of cisplatin, and up to 2.5-fold selectivity toward cancer cells over healthy fibroblasts. The presence of a redox-active dpp-Bian ligand in Pt and Pd complexes resulted in the induction of reactive oxygen species (ROS) in cancer cells. In addition, these complexes were able to intercalate into DNA, indicating the dual mechanism of action.

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“…The first redox process at −1.23 V for 3 and −0.98 V for 4 is irreversible, probably due to the elimination of Cl − . This is supported by the fact that an anodic peak appears on the CV curve at about 1.1 V, which is typical for the oxidation of Cl − [ 60 , 61 ]. The second process at −1.62 (ΔE = 130 mV) for 3 and −1.56 (ΔE = 110 mV) for 4 is quasi-reversible.…”

Section: Resultsmentioning

confidence: 87%

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties

et al. 2021

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A new monoiminoacenaphthenone 3,5-(CF3)2C6H3-mian (complex 2) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl2(dpp-mian)(CH3CN)] (3) and [VOCl(3,5-(CF3)2C6H3-bian)(H2O)][VOCl3(3,5-(CF3)2C6H3-bian)]·2.85DME (4) from [VOCl2(CH3CN)2(H2O)] (1) or [VCl3(THF)3]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex 4 has an unexpected structure. Firstly, it contains 3,5-(CF3)2C6H3-bian instead of 3,5-(CF3)2C6H3-mian. Secondly, it has a binuclear structure, in contrast to 3, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures 2 and 3, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36–3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes 3 and 4 has been proven by EPR spectroscopy. Complexes 3 and 4 exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex 3) and 27% (complex 4). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh3). According to the DFT calculations, the difference in the catalytic activity of 3 and 4 is most likely associated with a different mechanism for the generation of ·OH radicals. For complex 4 with electron-withdrawing CF3 substituents at the diimine ligand, an alternative mechanism, different from Fenton’s and involving a redox-active ligand, is assumed.

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A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour

Cited by 21 publications

References 82 publications

Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry

Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry

Heteroleptic Pd(II) and Pt(II) Complexes with Redox-Active Ligands: Synthesis, Structure, and Multimodal Anticancer Mechanism

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties

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