Phloroglucinol and resorcinol based mononuclear dioxidomolybdenum(VI) complexes: Synthesis, structural characterization and catalytic epoxidation

Maurya, Mannar R.; Rana, Lata; Avecilla, Fernando

doi:10.1016/j.poly.2017.01.006

Cited by 26 publications

(18 citation statements)

References 41 publications

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“…UV/Vis spectroscopic data (absorption maxima and respective extinction coefficients) of ligands and complexes are given in Table S3. Spectral studies of these ligands have been reported by us earlier and spectra of the complexes are presented in Figure . The transitions φ→φ*, π→π* and n→π* show slight variations upon coordination to vanadium due to rearrangement and electronic donation of the ligands.…”

Section: Resultsmentioning

confidence: 90%

“…Condensation of 4,6‐diacetyl resorcinol with various hydrazides in equimolar ratio in MeOH resulted in the formation of the analytically pure ligands H 2 dar‐inh ( I ), H 2 dar‐nah ( II ), H 2 dar‐bhz ( III ) and H 2 dar‐fah ( IV ) in good yields (68–72 %) (Scheme ) . An aqueous solution of in situ generated potassium vanadate (predominantly K[H 2 VO 4 ] at pH 7.0), obtained by dissolving V 2 O 5 in aqueous KOH, reacted with the potassium salt of these ligands giving the potassium salts of the corresponding dioxidovanadium(V) anions [K(H 2 O) 2 ][VO 2 (dar‐inh)] ( 1 ), [K(H 2 O) 2 ][VO 2 (dar‐nah)] ( 2 ), [K(H 2 O) 2 ][VO 2 (dar‐bhz)] ( 3 ) and [K(H 2 O) 2 ][VO 2 (dar‐fah)] ( 4 ), respectively – see Equation considering 2 as a representative complex.…”

Section: Resultsmentioning

confidence: 99%

“…Materials, Instrumentation and Physical Measurements: Chemicals and solvents used in this study were of analytical reagent grade and acquired from standard sources. Precursors [V IV O(acac) 2 ], 4,6‐diacetylresorcinol and ligands H 2 dar‐inh ( I ), H 2 dar‐nah ( II ), H 2 dar‐bhz ( III ) and H 2 dar‐fah ( IV ) were prepared according to methods reported in the literature. Elemental analysis (C, H and N) of ligands and complexes were performed in an Elementar Vario‐El‐III instrument.…”

Section: Methodsmentioning

confidence: 99%

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4,6‐Diacetyl Resorcinol Based Vanadium(V) Complexes: Reactivity and Catalytic Applications

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Four ONO donor ligands are isolated from the condensation of 4,6‐diacetyl resorcinol with isonicotinoyl hydrazide (H2dar‐inh, I), nicotinoyl hydrazide (H2dar‐nah, II), benzoyl hydrazide (H2dar‐bhz, III), and 2‐furoyl hydrazide (H2dar‐fah, IV) on refluxing in MeOH. The reaction of in situ generated aqueous K[H2VVO4] with ligands I–IV at neutral pH gives complexes [K(H2O)2][VO2(dar‐inh)] (1), [K(H2O)2][VO2(dar‐nah)] (2), [K(H2O)2][VO2(dar‐bhz)] (3), and [K(H2O)2][VO2(dar‐fah)] (4), respectively. The reaction of [VIVO(acac)2] (acac = acetylacetonato) with these ligands (I–IV) under aerobic conditions in methanol yields oxidomethoxidovanadium(V) complexes [VO(OMe)(MeOH)(dar‐inh)] (5), [VO(OMe)(MeOH)(dar‐nah)] (6), [VO(OMe)(MeOH)(dar‐bhz)] (7), and [VO(OMe)(MeOH)(dar‐fah)] (8). All the isolated complexes are characterized by elemental, thermal, electrochemical, and spectroscopic techniques [FTIR, UV/Vis, NMR (1H, 13C and 51 V NMR)], and single‐crystal X‐ray diffraction analysis (for 1, 6, 7, and 8). X‐ray analysis confirms the coordination of the ligands through Ophenolate, Nazomethine, and Oenolate to the metal center. In the molecular structure of [K(H2O)(EtOH)][VVO2(dar‐inh)] (abbreviated as 1a where one molecule of water is replaced by EtOH), water molecules act as bridges between two K+ ions and the complex shows a dimeric structure due to the presence of electrostatic interactions between V=O oxygen atoms with K+ ions. These complexes are active catalysts for the oxidative bromination of thymol in the presence of KBr, HClO4, and H2O2 and give 2‐bromothymol, 4‐bromothymol, and 2,4‐dibromothymol as major products. Complexes 1–4 were also tested as catalysts for the epoxidation of various alkenes (namely styrene, cyclohexene, cis‐cyclooctene, 1‐hexene, 1‐octene, cyclohexenone, and trans‐stilbene) with H2O2 in the presence of NaHCO3 as promoter, giving the corresponding epoxides selectively.

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Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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4,6‐Diacetyl Resorcinol Based Vanadium(V) Complexes: Reactivity and Catalytic Applications

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“…During recent decades, inspired of enzymatic role of molybdenum in biological systems such as oxotransferases (Xanthine oxidase, sulfite oxidase and DMSO reductase), significant attempts have been made to design various biomimetic Mo complexes as oxidation catalysts. In this regard, a number of ligands with N, O and S donor atoms which mimic proteins were synthesized and used in Mo coordination . Among various ligands, hydrazones, particularly acyl and aroyl hydrazones (‐CO‐NH‐N=CRR′; R and R′: H, alkyl, aryl) have attracted grate attention owing to their facile synthesis, structural diversities and chemical and biological activities .…”

Section: Introductionmentioning

confidence: 99%

“…In this regard, a number of ligands with N, O and S donor atoms which mimic proteins were synthesized and used in Mo coordination. [6][7][8][9] Among various ligands, hydrazones, particularly acyl and aroyl hydrazones (-CO-NH-N=CRR′; R and R′: H, alkyl, aryl) have attracted grate attention owing to their facile synthesis, structural diversities and chemical and biological activities. [10] These ligands contain amide (HN-C=O) moiety which gives them the possibility of enol-keto tautomerism providing the ligands coordinate the metal ions via neutral or anionic forms.…”

Section: Introductionmentioning

confidence: 99%

New magnetic supported hydrazone Schiff base dioxomolybdenum (VI) complex: An efficient nanocatalyst for epoxidation of cyclooctene and norbornene

Sarkheil

Lashanizadegan

2018

Applied Organom Chemis

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A new dioxomolybdenum (VI) complex with tridentate hydrazone Schiff base ligand (H2L) derived from 2‐hydroxy‐5‐nitrobenzaldehyde and benzhydrazide was synthesized and designated as [MoO2L (DMF)]·2H2O. The Fe3O4@SiO2‐CPS‐L‐MoO2 (EtOH) nanocatalyst was successfully prepared by grafting H2L ligand on modified Fe3O4 nanoparticles followed by reacting with MoO2 (acac)2. The complex and nanocatalyst were characterized by various techniques such as elemental analysis, mass, FT‐IR, UV–Vis, 1H NMR, 13C{1H}‐NMR, TGA, XRD, XPS, TEM, SEM and VSM. The catalytic activity of [MoO2L (DMF)]2H2O and Fe3O4@SiO2‐CPS‐L‐MoO2 (EtOH) were evaluated for the oxidation of various alkenes (cyclooctene, norbornene, cyclohexene, styrene and α‐methyl styrene) in the presence of tert‐butylhydroperoxide as oxidant. The results revealed that the catalysts were especially efficient for oxidation of cyclooctene and norbornene with 100% selectivity towards corresponding epoxide product. Fe3O4@SiO2‐CPS‐L‐MoO2 (EtOH) showed higher catalytic activity, shorter reaction time and higher turnover number (TON) compared with homogeneous complex [MoO2L (DMF)]·2H2O. Moreover, simple magnetic recovery from the reaction mixture and reuse for several times with no significant loss in activity were other advantages of the nanocatalyst.

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Two ionic oxo‐vanadate and dioxo‐molybdate complexes of dinitro‐aroylhydrazone derivative: Effective catalysts for epoxidation reactions, biological activity, ctDNA binding, density functional theory, andin silicoinvestigations

Adam

Shaaban

El‐Metwaly

2022

Applied Organom Chemis

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To meet the ecological demand for synthesis of ecofriendly metalated organic compounds, two new green dinitro‐aroylhydrazone derivatives (HLZNa) were used for the synthesis of vanadate(IV) and cis‐molybdate(VI) complexes (VOLZNa and MoO2LZNa). The N,O‐bidentate ligand and its M‐pincer chelates were characterized using various spectroscopic tools. Infrared spectra exhibited a high shift of the CH=N band with the disappearance of the O–H band of HLZNa after its coordination with V4+ and Mo6+ in VOLZNa and MoO2LZNa, respectively. 1H NMR spectra supported this observation for HLZNa compared with that of MoO2LZNa for the spectral signal of CH=N and O–H groups. In the UV–Vis. spectra, VOLZNa showed an additional spectral band at 741 nm for the d → d transition, which accomplished such complexation. Catalytically, VOLZNa exhibited slightly more catalytic action, with 92% yield after 2 h, compared with the MoO2LZNa catalyst (4 h with 92% yield) in the oxygenation of 1,2‐cyclooctene, that is, the epoxidation, at 90 °C. A strong reversible electrochemical behavior of VOLZNa (V4+/V5+redox couple) enhanced the catalytic action of VOLZNa over MoO2LZNa, which is supported by spectroscopic analysis. The biological behavior of HLZNa, VOLZNa, and MoO2LZNa was examined through their binding ability to ctDNA via UV–Vis. spectroscopy and hydrodynamic measurements. Spectroscopically, the derived binding constant of VOLZNa and MoO2LZNa (Kb = 4.45 and 5.01 × 108 mol−1 dm3, respectively) was higher than that of the free ligand (HLZNa, 2.88 × 108 mol−1 dm3), which is attributed to their reactivity toward ctDNA. Also, the Gibbs free energy values ( ∆Gb≠) for such an interaction illustrated their high potential against ctDNA over their ligand (−31.14, −32.22, and −32.52 kJ/mol for HLZNa, VOLZNa, and MoO2LZNa, respectively). The metal ions (V4+ and Mo6+) in VOLZNa and MoO2LZNa, respectively, improved their antioxidant, antimicrobial, and antitumor activities over the free ligand. The structures of the current compounds were further elucidated using the DFT/B3LYP method, which confirmed the mode of bonding depending on the distribution of the coordinating functional groups. Some physical parameters were estimated to evaluate the probability of these compounds' reactivity biologically and catalytically. The catalytic role of the MoO2LZNa complex was confirmed computationally. The in vitro obtains regarding the antimicrobial activity of the M‐chelates were tested using in silico approaches. The outcomes reflected the high conformity of VOLZNa as an effective antimicrobial reagent.

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Phloroglucinol and resorcinol based mononuclear dioxidomolybdenum(VI) complexes: Synthesis, structural characterization and catalytic epoxidation

Cited by 26 publications

References 41 publications

4,6‐Diacetyl Resorcinol Based Vanadium(V) Complexes: Reactivity and Catalytic Applications

4,6‐Diacetyl Resorcinol Based Vanadium(V) Complexes: Reactivity and Catalytic Applications

New magnetic supported hydrazone Schiff base dioxomolybdenum (VI) complex: An efficient nanocatalyst for epoxidation of cyclooctene and norbornene

Two ionic oxo‐vanadate and dioxo‐molybdate complexes of dinitro‐aroylhydrazone derivative: Effective catalysts for epoxidation reactions, biological activity, ctDNA binding, density functional theory, andin silicoinvestigations

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