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Title: Catalytic oxidation of internal and terminal alkenes by oxidoperoxidomolybdenum(VI) and dioxidomolybdenum(VI) complexes
Authors: Maurya, Mannar Ram
Rana L.
Avecilla F.
Published in: Inorganica Chimica Acta
Abstract: Reaction of oxidoperoxidomolybdenum(VI) species, generated in situ by the reaction of MoO3 in the presence of H2O2, with three Schiff bases H2hap-inh (I), H2hap-nah (II) and H2hap-bhz (III), (derived from the condensation of 2-hydroxyacetophenone with isonicotinoylhydrazide, nicotinoylhydrazide and benzoylhydrazide) results in the formation of oxidoperoxidomolybdenum(VI) complexes, [MoO(O2)(hap-inh)(MeOH)] (1), [MoO(O2)(hap-nah)(MeOH)] (2) and [MoO(O2)(hap-bhz)(MeOH)] (3), respectively. Their dioxidomolybdenum(VI) analogues [MoO2(hap-inh)]n (4) [MoO2(hap-nah)(MeOH)] (5) and [MoO2(hap-bhz)(MeOH)] (6) have also been prepared by reacting equimolar ratio of [MoO2(acac)2] and corresponding ligands. These complexes have been characterized in the solid state as well as in solution namely by spectroscopic techniques (IR, electronic, 1H and 13C NMR), elemental and thermogravimetric analysis. Structures of complexes 3, 4, and 6a ([MoO2(hap-bhz)(DMSO)]) have been confirmed by single crystal X-ray study which reveals that ligands behave as a dibasic tridentate coordinating through ONO functionalities. Sodium bicarbonate assisted oxidation of styrene and cyclohexene using 30% H2O2 as oxidant has been carried out using these catalysts. Under the optimized reaction conditions styrene gave mainly styrene oxide and minor amount of phenylacetaldehyde. Oxidation of cyclohexene gave cyclohexene epoxide selectively. The corresponding dioxidomolybdenum(VI) complexes have relatively lower catalytic activities. © 2015 Elsevier B.V. All rights reserved.
Citation: Inorganica Chimica Acta, 429: 138-147
Issue Date: 2015
Publisher: Elsevier S.A.
Keywords: Molybdenum(VI) complexes
NMR spectroscopy
Oxidation of cyclohexene
Oxidation of styrene
Tridentate ONO donor Schiff base ligands
ISSN: 201693
Author Scopus IDs: 7005255411
Author Affiliations: Maurya, M.R., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
Rana, L., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
Avecilla, F., Departamento de Química Fundamental, Universidade da Coruña, Campus de A Zapateira, A Coruña, 15071, Spain
Funding Details: One of the authors (L.T.) is thankful to Council of Scientific and Industrial Research, New Delhi for Junior Research Fellowship. Council of Scientific and Industrial Research, India, CSIR
Corresponding Author: Maurya, M.R.; Department of Chemistry, India; email:
Appears in Collections:Journal Publications [CY]

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