Dinuclear Mn(II, II) complexes: magnetic properties and microwave assisted oxidation of alcohols

被引:65
作者
Sutradhar, Manas [1 ]
Martins, Luisa M. D. R. S. [1 ,2 ]
Guedes da Silva, M. Fatima C. [1 ]
Alegria, Elisabete C. B. A. [1 ,2 ]
Liu, Cai-Ming [3 ]
Pombeiro, Armando J. L. [1 ]
机构
[1] Univ Lisbon, Inst Super Tecn, Ctr Quim Estrutural, P-1049001 Lisbon, Portugal
[2] ISEL, Dept Chem Engn, P-1959007 Lisbon, Portugal
[3] Chinese Acad Sci, Inst Chem, Ctr Mol Sci, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
关键词
MONONUCLEAR OXIDOVANADIUM(V) COMPLEX; ELECTRON-PARAMAGNETIC-RESONANCE; EFFICIENT FUNCTIONAL-MODEL; SCHIFF-BASE COMPLEX; AEROBIC OXIDATION; CATALYTIC-ACTIVITY; COPPER(II) COMPLEXES; BENZYLIC ALCOHOLS; SALEN COMPLEXES; MANGANESE;
D O I
10.1039/c3dt52774c
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A series of six new mixed-ligand dinuclear Mn(II, II) complexes of three different hydrazone Schiff bases (H3L1, H3L2 and H3L3), derived from condensation of the aromatic acid hydrazides benzohydrazide, 2-aminobenzohydrazide or 2-hydroxybenzohydrazide, with 2,3-dihydroxy benzaldehyde, respectively, is reported. Reactions of Mn(NO3)(2) center dot 4H(2)O with the H3L1-3 compounds, in the presence of pyridine (1 : 1 : 1 mole ratio), in methanol at room temperature, yield [Mn(H2L1)(py)(H2O)](2)(NO3)(2) center dot 2H(2)O (1 center dot 2H(2)O), [Mn(H2L2)(py)(CH3OH)](2)(NO3)(2) center dot 4H(2)O (2 center dot 4H(2)O) and [Mn(H2L3)(py)(H2O)](2)(NO3)(2) (3) respectively, whereas the use of excess pyridine yields complexes with two axially coordinated pyridine molecules at each Mn(II) centre, viz. [Mn(H2L1)(py)(2)] 2(NO3)(2) center dot H2O (4 center dot H2O), [Mn(H2L2)(py) H-O (6 center dot 2CH(3)OH), respectively. In all the complexes, the (H2L1-3)-ligand coordinates in the keto form. Complexes 1 center dot 2H(2)O, 2 center dot 4H(2)O, 4 center dot H2O, 5 center dot 2H(2)O and 6 center dot 2CH(3)OH are characterized by single crystal X-ray diffraction analysis. The complexes 1, 2 and 6, having different coordination environments, have been selected for variable temperature magnetic susceptibility measurements to examine the nature of magnetic interaction between magnetically coupled Mn(II) centres and also for exploration of the catalytic activity towards microwave assisted oxidation of alcohols. A yield of 81% (acetophenone) is obtained using a maximum of 0.4% molar ratio of catalyst relative to the substrate in the presence of TEMPO and in aqueous basic solution, under mild conditions.
引用
收藏
页码:3966 / 3977
页数:12
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