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Pentacoordinated copper-sparteine complexes with chelating nitrite or nitrate ligand: Synthesis and catalytic aspects

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Title Pentacoordinated copper-sparteine complexes with chelating nitrite or nitrate ligand: Synthesis and catalytic aspects
 
Creator INDRA, A
MOBIN, SM
BHADURI, S
LAHIRI, GK
 
Subject SELECTIVE OXIDATION
MODEL COMPLEXES
(-)-SPARTEINE
BENZALDEHYDE
STYRENE
DERIVATIVES
EPOXIDATION
COBALT(II)
REDUCTASE
PHASE
Copper
Sparteine
EPR spectra
Crystal structure
Catalysis
 
Description Copper(II)-sparteine complexes, [Cu(II){(-)Sp}(NO(2))Cl] (1) and [Cu(II){(-)Sp}(NO(3))Cl] (2) (Sp = sparteine) with chelating nitrite and nitrate ligands, respectively, have been synthesized and structurally characterized. The penta-coordinated 1 or 2 exhibits distorted square pyramidal geometry and shows characteristic EPR spectra with g(parallel to): 2.27 and g(perpendicular to): 2.06. 1 and 2 behave similarly towards the catalytic epoxidation of alkenes as well as oxidation of alcohols. Though the epoxidation of cyclohexene using 1 or 2 as a catalyst and tertiarybutyl hydroperoxide (TBHP) as an oxidant at 298 K in acetonitrile results in 100% cyclohexene oxide product, under identical reaction conditions styrene selectively transforms to benzaldehyde (similar to 90%) instead of any styrene oxide. However, at higher temperature (353 K) the selectivity of cyclohexene to corresponding epoxide formation decreases appreciably and additional products, cyclohexanol and cyclohexanone are formed. Furthermore, 1 or 2 effectively catalyzes the oxidation of benzyl alcohol to benzoic acid and cyclohexanol to cyclohexanone in presence of molecular oxygen (O(2)) as an oxidant at 353 K in acetonitrile. (C) 2011 Elsevier B. V. All rights reserved.
 
Publisher ELSEVIER SCIENCE SA
 
Date 2012-06-26T06:59:58Z
2012-06-26T06:59:58Z
2011
 
Type Article
 
Identifier INORGANICA CHIMICA ACTA,374(1)415-421
0020-1693
http://dx.doi.org/10.1016/j.ica.2011.03.027
http://dspace.library.iitb.ac.in/jspui/handle/100/14079
 
Language English