Redox chemistry of copper complexes with various salen type ligands

被引:32
作者
Butsch, Katharina [1 ]
Guenther, Thomas [2 ]
Klein, Axel [1 ]
Stirnat, Kathrin [1 ]
Berkessel, Albrecht [2 ]
Neudoerfl, Joerg [2 ]
机构
[1] Univ Cologne, Inst Anorgan Chem, Dept Chem, D-50939 Cologne, Germany
[2] Univ Cologne, Inst Organ Chem, Dept Chem, D-50939 Cologne, Germany
关键词
Salen ligands; Copper(II); Electrochemistry; EPR; Spectroelectrochemistry; Alcohol oxidation; CATALYZED ASYMMETRIC EPOXIDATION; X-RAY STRUCTURES; GALACTOSE-OXIDASE; SCHIFF-BASE; PRIMARY ALCOHOLS; KINETIC RESOLUTION; HYDROGEN-PEROXIDE; HENRY REACTION; ACTIVE-SITE; OXIDATION;
D O I
10.1016/j.ica.2012.08.016
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The two essential redox processes in Cu(II) salen (and salan) complexes Cu(II)/Cu(I) and [PhO](center dot)/[PhO[-]] were studied by electrochemical and spectroelectrochemical (UV-Vis-absorption or EPR) techniques on a series of complexes in which the salen (salan) type ligands bear various substituents R = H, F, Ph, tBu or CH3 on the linker C- or N-atoms or on the phenol core. The substitution pattern can be related to the stability of the phenoxy radicals. The geometry of the complexes (especially around the Cu atom) could be established by XRD for the new complex [(Me(2)salhexF(4))Cu] {H-2(Me(2)salhexF(4)) = (1R,2R)-N,N'-bis(2-hydroxy-3,5-di-fluoro-acetophenonylidene)-cyclohexane-1,2-diamine} in the solid and for all other derivatives by EPR in fluid solution. Also, the application of the complexes in oxidation catalysis was tested using the oxidation of benzyl alcohol. (C) 2012 Elsevier B. V. All rights reserved.
引用
收藏
页码:237 / 246
页数:10
相关论文
共 104 条
[11]   A phenol-imidazole pro-ligand that can exist as a phenoxyl radical, alone and when complexed to copper(II) and zinc(II) [J].
Benisvy, L ;
Blake, AJ ;
Collison, D ;
Davies, ES ;
Garner, CD ;
McInnes, EJL ;
McMaster, J ;
Whittaker, G ;
Wilson, C .
DALTON TRANSACTIONS, 2003, (10) :1975-1985
[12]   Combinatorial approaches to functional models for galactose oxidase [J].
Berkessel, A ;
Dousset, M ;
Bulat, S ;
Glaubitz, K .
BIOLOGICAL CHEMISTRY, 2005, 386 (10) :1035-1041
[13]   Mass-spectrometric and kinetic studies on the mechanism and degradation pathways of titanium salalen catalysts for asymmetric epoxidation with aqueous hydrogen peroxide [J].
Berkessel, Albrecht ;
Brandenburg, Marc ;
Schaefer, Mathias .
ADVANCED SYNTHESIS & CATALYSIS, 2008, 350 (09) :1287-1294
[14]   EFFECTS ON MOLECULAR ASSOCIATION, CHELATE CONFORMATION, AND REACTIVITY TOWARD SUBSTITUTION IN CU(5-X-SALEN) COMPLEXES, SALEN2- = N,N'-ETHYLENEBIS(SALICYLIDENAMINATO), X = H, CH3O, AND CL - SYNTHESIS, X-RAY STRUCTURES, AND EPR INVESTIGATIONS [J].
BHADBHADE, MM ;
SRINIVAS, D .
INORGANIC CHEMISTRY, 1993, 32 (24) :5458-5466
[15]   Titanium-salan-catalyzed asymmetric oxidation of sulfides and kinetic resolution of sulfoxides with H2O2 as the oxidant [J].
Bryliakov, Konstantin P. ;
Talsi, Evgenii P. .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2008, 2008 (19) :3369-3376
[16]   Chiral Schiff base complexes of copper(II), vanadium(IV) and nickel(II) as oxidation catalysts.: X-ray crystal structures of [Cu(R-salpn)(OH2)] and [Cu(±-busalcx)] [J].
Bunce, S ;
Cross, RJ ;
Farrugia, LJ ;
Kunchandy, S ;
Meason, LL ;
Muir, KW ;
O'Donnell, M ;
Peacock, RD ;
Stirling, D ;
Teat, SJ .
POLYHEDRON, 1998, 17 (23-24) :4179-4187
[17]   A stable aminyl radical metal complex [J].
Büttner, T ;
Geier, J ;
Frison, G ;
Harmer, J ;
Calle, C ;
Schweiger, A ;
Schönberg, H ;
Grützmacher, H .
SCIENCE, 2005, 307 (5707) :235-238
[18]   Utilisation of homogeneous and supported chiral metal(salen) complexes in asymmetric catalysis [J].
Canali, L ;
Sherrington, DC .
CHEMICAL SOCIETY REVIEWS, 1999, 28 (02) :85-93
[19]   Biomimetic metal-radical reactivity:: aerial oxidation of alcohols, amines, aminophenols and catechols catalyzed by transition metal complexes [J].
Chaudhuri, P ;
Wieghardt, K ;
Weyhermüller, T ;
Paine, TK ;
Mukherjee, S ;
Mukherjee, C .
BIOLOGICAL CHEMISTRY, 2005, 386 (10) :1023-1033
[20]   Aerobic oxidation of primary alcohols (including methanol) by copper(II)- and zinc(II)-phenoxyl radical catalysts [J].
Chaudhuri, P ;
Hess, M ;
Müller, J ;
Hildenbrand, K ;
Bill, E ;
Weyhermüller, T ;
Wieghardt, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9599-9610