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Title: Study of temperature dependent three component dynamic covalent assembly VIa Hantzsch reaction catalyzed by dioxido- and oxidoperoxidomolybdenum(VI) complexes under solvent free conditions
Authors: Maurya, Mannar Ram
Saini N.
Avecilla F.
Published in: RSC Advances
Abstract: Tridentate ONO donor ligands derived from heterocyclic compound 4-acetyl-3-methyl-1-phenyl-2-pyrazoline-5-one (Hap) and aromatic hydrazides {benzoyl hydrazide (Hbhz), isonicotinoyl hydrazide (Hinh), nicotinoyl hydrazide (Hnah) and furoyl hydrazide (Hfah)} react with [MoVIO2(acac)2] (Hacac = acetylacetone) in equimolar ratio in methanol to give dioxidomolybdenum(vi) complexes, [MoO2(ap-bhz)(MeOH)] 1, [MoO2(ap-inh)(MeOH)] 2, [MoO2(ap-nah)(MeOH)] 3 and [MoO2(ap-fah)(MeOH)] 4. Reaction of these ligands with in situ generated oxidoperoxidomolybdenum(vi) precursor results in the formation of oxidoperoxidomolybdenum(vi) complexes, [MoO(O2)(ap-bhz)(MeOH)] 5, MoO(O2)(ap-inh)(MeOH)] 6, MoO(O2)(ap-nah)(MeOH)] 7 and MoO(O2)(ap-fah)(MeOH)] 8. These complexes have been characterized by elemental analysis, spectroscopic techniques (infrared, UV-vis, 1H and 13C NMR) and thermogravemetric analysis. The structures of complexes [MoVIO2(ap-bhz)(H2O)] 1a (water coordinated), [MoVIO2(ap-bhz)(DMSO)] 1b (DMSO coordinated), [MoVIO2(ap-nah)(DMF)] 3a (DMF coordinated), [MoVIO(O2)(ap-bhz)(MeOH)] 5 (methanol coordinated) and [MoVIO(O2)(Hap-nah)(OMe)]·MeOH 7a (methoxy coordinated) have been confirmed by single crystal X-ray studies. X-ray diffraction study also reveals that tridentate ligands bind to the metal center through enolic oxygen (of pyrazolol), azomethine nitrogen and enolic oxygen (of hydrazide) atoms. In complex 7a, pyridinic nitrogen is protonated. These complexes [dioxidomolybdenum(vi) as well as oxidoperoxidomolybdenum(vi)] have been tested as catalysts for temperature dependent one pot three component (methylacetoacetate, benzaldehyde and ammonium acetate) dynamic covalent assembly, via Hantzsch reaction, using 30% H2O2 as a green oxidant under solvent free conditions. Various parameters such as the amount of catalyst, oxidant and temperature of the reaction mixture have been taken into consideration to optimize the reaction conditions. In the Hantzsch reaction, the temperature and oxidant control the conversion and selectivity of the desired product. © The Royal Society of Chemistry 2016.
Citation: RSC Advances, 6(16): 12993-13009
Issue Date: 2016
Publisher: Royal Society of Chemistry
Keywords: Acetone
Molybdenum compounds
Molybdenum oxide
Nuclear magnetic resonance spectroscopy
Single crystals
Spectroscopic analysis
X ray diffraction
Covalent assemblies
Heterocyclic compound
Methyl acetoacetate
Reaction conditions
Solvent free conditions
Spectroscopic technique
Temperature dependent
X-ray diffraction studies
Coordination reactions
ISSN: 20462069
Author Scopus IDs: 7005255411
Author Affiliations: Maurya, M.R., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247 667, India
Saini, N., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247 667, India
Avecilla, F., Departamento de Química Fundamental, Universidade da Coruña, Campus de A Zapateira, Coruña, 15071 A, Spain
Funding Details: 
Corresponding Author: Maurya, M.R.; Department of Chemistry, India; email:
Appears in Collections:Journal Publications [CY]

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