New oxidovanadium(<scp>iv</scp>) complex with a BIAN ligand: synthesis, structure, redox properties and catalytic activity

Fomenko, Iakov S.; Gushchin, Artem L.; Shul’pina, Lidia S.; Ikonnikov, Nikolay S.; Abramov, Pavel A.; Romashev, Nikolay F.; Poryvaev, Artem S.; Sheveleva, Alena M.; Bogomyakov, A. S.; Shmelev, Nikita Y.; Fedin, Matvey V.; Shul’pin, Georgiy B.; Sokolov, Maxim N.

doi:10.1039/c8nj03358g

Cited by 43 publications

(32 citation statements)

References 116 publications

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“…A ferromagnetic intermolecular interaction between the molecules in the chains of polymeric oxidovanadium(IV) complexes with tetradentate Schiff base ligands have been found [39]. The IR spectra of the complexes 1-4a show a strong V = O stretching band around 880-890 cm −1 which is typical for linear chain V = O…V = O polymeric structures [34][35][36][37][38][39] This band is significantly blue-shifted in the IR spectra of monomeric oxidovanadium complexes [63][64][65][66]. A ferromagnetic intermolecular interaction between the molecules in the chains of polymeric oxidovanadium(IV) complexes with tetradentate Schiff base ligands have been found [39].…”

Section: Synthesis and Characterization Of Compounds 1-4amentioning

confidence: 92%

“…Vanadium trichloride adduct with tetrahydrofuran ([VCl 3 (thf) 3 ]) and vanadium tribromide (VBr 3 ) were used as starting compounds which were oxidized during the reaction in air to give the V = O moiety (Scheme 1). This synthetic procedure was previously applied for the synthesis of other oxidovanadium(IV) complexes with chiral dehydrophenanthroline and diazofluorene ligands as well as with the redox-active bis(N-(2,6-diisopropylphenyl)imino)acenaphthene (dpp-bian) ligand [25,63]. The reactions of the corresponding vanadium precursor and 2,2 -bipyridine (bpy) or 1,10-phenanthroline (phen) in a 1:1 molar ratio resulted in microcrystalline products in yields ranging from moderate to high.…”

Section: Synthesis and Characterization Of Compounds 1-4amentioning

confidence: 99%

“…Very recently, we have reported the synthesis of monomeric square-pyramidal oxidovanadium(IV) complex ([VOCl 2 (dpp-bian)]) with the redox-active bis[N-(2,6-diisopropylphenyl)imino]acenaphthene ligand (dpp-bian). The complex demonstrated a high catalytic activity towards alkane oxygenation by H 2 O 2 under mild conditions [63]. Expanding that work, herein, we carried out reactions of [VCl 3 (thf) 3 ] or VBr 3 with heterocyclic diimines such as 2,2 -bipyridine and 1,10-phenanthroline to yield polymeric oxidovanadium(IV) complexes [VO(L)X 2 ] n (L = bpy, phen and X = Cl, Br) and studied their catalytic properties in alkane and alcohol oxidation reactions with peroxides.…”

Section: Introductionmentioning

confidence: 99%

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New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

et al. 2019

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Reactions of [VCl3(thf)3] or VBr3 with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) in a 1:1 molar ratio in air under solventothermal conditions has afforded polymeric oxidovanadium(IV) four complexes 1–4 of a general formula [VO(L)X2]n (L = bpy, phen and X = Cl, Br). Monomeric complex [VO(DMF)(phen)Br2] (4a) has been obtained by the treatment of compound 4 with DMF. The complexes were characterized by IR spectroscopy and elemental analysis. The crystal structures of 3 and 4a were determined by an X-ray diffraction (XRD) analysis. The {VOBr2(bpy)} fragments in 3 form infinite chains due to the V = O…V interactions. The vanadium atom has a distorted octahedral coordination environment. Complexes 1–4 have been tested as catalysts in the homogeneous oxidation of alkanes (to produce corresponding alkyl hydroperoxides which can be easily reduced to alcohols by PPh3) and alcohols (to corresponding ketones) with H2O2 or tert-butyl hydroperoxide in MeCN. Compound 1 exhibited the highest activity. The mechanism of alkane oxidation was established using experimental selectivity and kinetic data and theoretical DFT calculations. The mechanism is of the Fenton type involving the generation of HO• radicals.

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Section: Synthesis and Characterization Of Compounds 1-4amentioning

confidence: 92%

Section: Synthesis and Characterization Of Compounds 1-4amentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

et al. 2019

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“…The proposed model is also in agreement with the experimental data. Gushchin, Kuznetsov, et al recently [84,85] observed high activity among the vanadium complexes shown in Scheme 5 in the oxidation of hydrocarbons with peroxides. The mechanism for the generation of OH radicals is presented in Scheme 6.…”

Section: Oxidation Of Hydrocarbons and Alcohols With Peroxides Catalymentioning

confidence: 96%

“…Machura et al [79] described the oxidation of inert alkanes to alkyl hydroperoxides by H2O2 catalyzed with monomeric oxovanadium(V) complexes of 8-hydroxyquinoline derivatives as noninnocent ligands (Scheme 4). The analogous ligands in complexes with copper or rhenium were used in oxidations by peroxides [80][81][82][83] Gushchin, Kuznetsov, et al recently [84,85] observed high activity among the vanadium complexes shown in Scheme 5 in the oxidation of hydrocarbons with peroxides. The mechanism for the generation of OH radicals is presented in Scheme 6.…”

Section: Oxidation Of Hydrocarbons and Alcohols With Peroxides Catalymentioning

confidence: 99%

Metal Complexes Containing Redox-Active Ligands in Oxidation of Hydrocarbons and Alcohols: A Review

2019

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Ligands are innocent when they allow oxidation states of the central atoms to be defined. A noninnocent (or redox) ligand is a ligand in a metal complex where the oxidation state is not clear. Dioxygen can be a noninnocent species, since it exists in two oxidation states, i.e., superoxide (O2−) and peroxide (O22−). This review is devoted to oxidations of C–H compounds (saturated and aromatic hydrocarbons) and alcohols with peroxides (hydrogen peroxide, tert-butyl hydroperoxide) catalyzed by complexes of transition and nontransition metals containing innocent and noninnocent ligands. In many cases, the oxidation is induced by hydroxyl radicals. The mechanisms of the formation of hydroxyl radicals from H2O2 under the action of transition (iron, copper, vanadium, rhenium, etc.) and nontransition (aluminum, gallium, bismuth, etc.) metal ions are discussed. It has been demonstrated that the participation of the second hydrogen peroxide molecule leads to the rapture of O–O bond, and, as a result, to the facilitation of hydroxyl radical generation. The oxidation of alkanes induced by hydroxyl radicals leads to the formation of relatively unstable alkyl hydroperoxides. The data on regioselectivity in alkane oxidation allowed us to identify an oxidizing species generated in the decomposition of hydrogen peroxide: (hydroxyl radical or another species). The values of the ratio-of-rate constants of the interaction between an oxidizing species and solvent acetonitrile or alkane gives either the kinetic support for the nature of the oxidizing species or establishes the mechanism of the induction of oxidation catalyzed by a concrete compound. In the case of a bulky catalyst molecule, the ratio of hydroxyl radical attack rates upon the acetonitrile molecule and alkane becomes higher. This can be expanded if we assume that the reactions of hydroxyl radicals occur in a cavity inside a voluminous catalyst molecule, where the ratio of the local concentrations of acetonitrile and alkane is higher than in the whole reaction volume. The works of the authors of this review in this field are described in more detail herein.

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Redox‐active BIAN‐based Diimine Ligands in Metal‐Catalyzed Small Molecule Syntheses**

2021

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Dedicated to Kilian Munizα-Diimine ligands have significantly shaped the coordination chemistry of most transition metal complexes. Among them, bis (imino)acenaphthene ligands (BIANs) have recently been matured to great versatility and applicability to catalytic reactions. Besides variations of the ligand periphery, the great versatility of BIAN ligands resides within their ability to undergo facile electronic manipulations. This review highlights key aspects of BIAN ligands in metal complexes and summarizes recent contributions of metal-BIAN catalysts to syntheses of small and functionalized organic molecules.

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New oxidovanadium(iv) complex with a BIAN ligand: synthesis, structure, redox properties and catalytic activity

Abstract: The combination of a new oxidovanadium(iv) complex1with pyrazine-2-carboxylic acid (PCA; a cocatalyst) affords a catalytic system for the efficient oxidation of saturated hydrocarbons.

Cited by 43 publications

References 116 publications

New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

Metal Complexes Containing Redox-Active Ligands in Oxidation of Hydrocarbons and Alcohols: A Review

Redox‐active BIAN‐based Diimine Ligands in Metal‐Catalyzed Small Molecule Syntheses**

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