Charged dioxomolybdenum(VI) complexes with pyridoxal thiosemicarbazone ligands as molybdenum(V) precursors in oxygen atom transfer process and epoxidation (pre)catalysts

Pisk, Jana; Prugovečki, Biserka; Matković‐Čalogović, Dubravka; Poli, Rinaldo; Agustin, Dominique; Vrdoljak, Višnja

doi:10.1016/j.poly.2011.12.003

Cited by 68 publications

(31 citation statements)

References 84 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Some molybdates show antiviral, antitumoral or antibiotic activity [5][6][7]. They are also known as efficient catalysts for the oxidation of various organic compounds with different oxygen donors like ROOH [8][9][10][11][12][13][14][15][16][17][18][19][20] and H 2 O 2 [21][22][23][24][25][26][27][28][29]. Molybdenum(VI) dioxo or oxodiperoxo compounds are commonly encountered in oxidation catalysis.…”

Section: Introductionmentioning

confidence: 99%

“…It has been shown that mononuclear peroxo and mono-oxo bridged dinuclear molybdenum complexes are active catalysts for the epoxidation of olefins and nonfunctionalized olefins with t-butylhydroperoxide TBHP as oxygen donor [8,[13][14][15]. The epoxidation of olefins catalyzed by a large family of complexes with MoO 2 X 2 (N-N) 2 or MoO 2 X 2 (N-O) 2 formula where N-N or N-O are bidenate ligands and X = Cl, Br or Me has been previously reported [10,11,15,16]. All these catalysts show high activity and selectivity.…”

Section: Introductionmentioning

confidence: 99%

“…Molybdenum oxo and oxo-peroxo complexes have been used for selective oxidation of amines [13,[30][31][32][33] and for oxidation of allylic alcohols with H 2 O 2 [34]. Dioxomolybdenum(VI) complexes with a N-salicylidene amino acid hydrazide [28] or oxazoline [16] ligand were applied for oxidation of sulfides with high selectivity to sulfoxides. Dioxomolybdenum(VI) complexes of the MoO 2 L 2 type (L = (2 0 -pirydyl)alcoholate) were used as catalysts for the selective terminal oxidation of n-alkanes with molecular oxygen [35].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

et al. 2016

View full text Add to dashboard Cite

A group of new polymolybdates was synthesized and tested in the catalytic oxidation of cycloalkanes. Investigated compounds exhibit broad structural diversity including polymolybdates with isolated anionic clusters (0-dim), polymeric anions (1-dim), Mo-O layers (2-dim) as well as hexagonal and orthorhombic molybdenum oxides (3-dim). All studied molybdenum complexes were found to be active in the reaction conditions yielding ketones and alcohols as main products. In the case of layered compounds (2-dim), dicarboxylic acid was detected in the mixture of reaction products. The structure of investigated molybdenum compounds was shown to have influence on yields and selectivities of the investigated reactions. Anionic layers separation (in 2-dim materials) as well as type and charge of organic cations present in the compounds are prime examples of structural factors influencing the oxidation reactions efficiencies. On the basis of obtained results and literature reports a mechanism for the oxidation of cycloalkanes by polymolybdates has been proposed. Graphical Abstract

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Molybdenum thiosemicarbazone complexes have attracted much interest due to their unique advantages in forming compound type MoO 2 L which possess one "open" coordination sites that can be utilized for substrate binding [1], [2]. Therefore, the mononuclear dioxomolybdenum complexes might be interesting model systems.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Spectroscopic and Quantum Chemical Studies of a Novel Cis-dioxomolybdenum(vi) Thiosemicarbazonate Complex

İlhan-Ceylan¹,

Yılmaz²,

Yalçinkaya³

et al. 2016

IJCEA

View full text Add to dashboard Cite

“…[24] In particular, thiosemicarbazones derived from salicylaldehydes allow a systematic investigation of the effect of electron-withdrawing groups (EWGs) or electron-donating groups (EDGs) on the electronic properties of a coordinated molybdenum center. It was found that these electronic trends are reflected in the spectroscopic properties of the molybdenum complexes formed, [18,25] and in their catalytic, [26] biological, [27,28] and pharmacological properties. [29,30] Here we present the synthesis, characterization and catalytic OAT activity of a series of cis-dioxomolybdenum(VI) complexes with structurally related tridentate thiosemicarbazone ligands (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

Electronic Fine‐Tuning of Oxygen Atom Transfer Reactivity of cis‐Dioxomolybdenum(VI) Complexes with Thiosemicarbazone Ligands

et al. 2015

View full text Add to dashboard Cite

A series of six cis‐dioxomolybdenum(VI) complexes with thiosemicarbazone ligands was synthesized and characterized. The ligands were obtained by reacting ethyl thiosemicarbazide with salicylaldehydes substituted with a selection of electron‐withdrawing and electron‐donating groups. The crystal structures, IR, NMR spectroscopic data and oxygen atom transfer activities of the complexes revealed that the electronic effects of the substituents located in the para‐position of the phenolate donor are transmitted through to the molybdenum center, as reflected by linear relationships between Hammett constants and key properties of the complexes, including the molybdenum–phenolate bond lengths and the coordination shift of the imine proton resonance. Compared with the unsubstituted catalyst, electron‐withdrawing substituents increase the rate of oxygen atom transfer from dimethyl sulfoxide to triphenylphosphine, whereas electron‐donating groups have the opposite effect. The highest rate enhancement was achieved through the introduction of a strongly electron‐withdrawing NO2 substituent in the p‐position of the phenolate donor.

show abstract

Charged dioxomolybdenum(VI) complexes with pyridoxal thiosemicarbazone ligands as molybdenum(V) precursors in oxygen atom transfer process and epoxidation (pre)catalysts

Cited by 68 publications

References 84 publications

Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

Synthesis, Spectroscopic and Quantum Chemical Studies of a Novel Cis-dioxomolybdenum(vi) Thiosemicarbazonate Complex

Electronic Fine‐Tuning of Oxygen Atom Transfer Reactivity of cis‐Dioxomolybdenum(VI) Complexes with Thiosemicarbazone Ligands

Contact Info

Product

Resources

About