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Structural variation and magneto-structural correlation in two new dinuclear bis(μ2-phenoxo)-bridged CuII Schiff-base complexes: catalytic potential for the peroxidative oxidation of cycloalkanes

Basak, Subhra and Sen, Soma and Roy, Partha and Butcher, Ray J. and Hughes, David L. and Gómez-García, Carlos J. and Garribba, Eugenio and Mitra, Samiran (2010) Structural variation and magneto-structural correlation in two new dinuclear bis(μ2-phenoxo)-bridged CuII Schiff-base complexes: catalytic potential for the peroxidative oxidation of cycloalkanes. Australian Journal of Chemistry, Vol. 63 (3), p. 479-489. eISSN 1445-0038. Article.

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DOI: 10.1071/CH09396

Abstract

Two new dinuclear bis(μ2-phenoxo)-bridged copper(II) complexes [Cu(NCS)L1]2 (1) and [Cu(NCS)L2]2 (2) have been synthesized using two tridentate NNO-donor Schiff-base ligands, L1H (Me2N(CH2)3N=CHC6H3(OMe)(OH)) and L2H (Me2N(CH2)3N=C(CH3)C6H4(OH)), respectively. They have been characterized by elemental analyses, IR, UV-visible, and electron paramagnetic resonance (EPR) spectroscopy, cyclic voltammetry, and magnetic susceptibility measurements. X-Ray single-crystal structures reveal a central Cu2O2 core in each complex with an isothiocyanate ligand coordinated terminally to each metal centre. The coordination environments around the CuII ions in 1 and 2 are a distorted trigonal bipyramid and a quasi-regular square pyramid, respectively, with significant differences in the Cu–O–Cu bridging angles (100.22(5)° for 1 and 95.64(7)° for 2). Although both CuII dimers present intradimer antiferromagnetic exchange interactions, the magnitudes of the coupling constants in 1 and 2 (J = –119(1) and –0.361(3) cm–1, respectively) are quite different as a result of the different coordination geometries and Cu–O–Cu bridging angles. Both complexes act as promising catalysts or catalyst precursors for the efficient peroxidative oxidation of cycloalkanes (cyclohexane and cycloheptane) to the corresponding cyclic alcohols and ketones, with maximum overall yields of 53% and 56% for 1 and 2, respectively.

Item Type:Article
ID Code:3738
Status:Published
Refereed:Yes
Uncontrolled Keywords:Magneto-structural correlation, structural variation, peroxidative oxidation, cycloalkanes
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:CSIRO Publishing
eISSN:1445-0038
Deposited On:16 Apr 2010 11:20

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