Structural studies on manganese(III) and manganese(IV) complexes of tetrachlorocatechol and the catalytic reduction of dioxygen to hydrogen peroxide

被引:23
作者
Sheriff, TS
Carr, P
Coles, SJ
Hursthouse, MB
Lesin, J
Light, ME
机构
[1] Univ London Queen Mary Coll, Dept Chem, Inorgan Chem Res Lab, London E1 4NS, England
[2] Univ Hertfordshire, Sch Chem, Hatfield AL10 9AB, Herts, England
[3] Univ Southampton, Dept Chem, Southampton SO17 1BJ, Hants, England
关键词
manganese; tetrachlorocatechol; catecholate complexes; hydrogen peroxide; hydroxylamine; dioxygen activation catalyst;
D O I
10.1016/j.ica.2003.09.032
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The mononuclear complexes (Bu4N)[Mn(Cl(4)Cat)(2)(H2O)(EtOH)] and (Bu4N)(2)[Mn(Cl(4)Cat)(3)] (H(2)Cat = 1,2-dihydroxybenzene) have been synthesised and characterised by X-ray diffraction. This work provides a direct, independent, synthesis of these complexes and an interesting example of how solvent effects can promote the formation of either a manganese(III) or manganese(IV) complex of the same ligand. The characterisation of (Bu4N)[Mn(Cl(4)Cat)(2)(H2O)(EtOH)] supports previous work that manganese(III) is extremely reluctant to form tris (catecholato) complexes due to the short 'bite distance' of catecholate oxygen atoms (2.79 Angstrom) which are unable to span the elongated coordination axes of the Jahn-Teller distorted Mn(III) ion and explains the 2:1 and 3:1 tetrachlorocatechol: manganese ratios in the Mn(III) and Mn(IV) complexes, respectively. Hydrogen peroxide production using dioxygen and hydroxylamine as substrates in acetonitrile/water mixtures, under ambient conditions, can be demonstrated with both complexes, suggesting that neither labile coordination sites nor the oxidation state of the manganese are important to the catalytic system. Turn over frequencies (TOF, moles of H2O2, per moles of manganese per hour) of similar to10000 h(-1) are obtained and this compares very favourably with the commercial production of hydrogen peroxide by the autoxidation of 2-ethylanthrahydroquinone (AO process). (C) 2003 Elsevier B.V. All rights reserved.
引用
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页码:2494 / 2502
页数:9
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