Syntheses and structural characterization of dinuclear and tetranuclear iron(III) complexes with dinucleating ligands and their reactions with hydrogen peroxide.
The iron(III) complexes [Fe(2)(HPTB)(mu-OH)(NO(3))(2)](NO(3))(2).CH(3)OH.2H(2)O (1), [Fe(2)(HPTB)(mu-OCH(3))(NO(3))(2)](NO(3))(2).4.5CH(3)OH (2), [Fe(2)(HPTB)(mu-OH)(OBz)(2)](ClO(4))(2).4.5H(2)O (3), [Fe(2)(N-EtOH-HPTB)(mu-OH)(NO(3))(2)](ClO(4))(NO(3)).3CH(3)OH.1.5H(2)O (4), [Fe(2)(5,6-Me(2)-HPTB)(mu-OH)(NO(3))(2)](ClO(4))(NO(3)).3.5CH(3)OH.C(2)H(5)OC(2)H(5).0.5H(2)O (5), and [Fe(4)(HPTB)(2)(mu-F)(2)(OH)(4)](ClO(4))(4).CH(3)CN.C(2)H(5)OC(2)H(5).H(2)O (6) were synthesized (HPTB = N,N,N',N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane, N-EtOH-HPTB = N,N,N',N'-tetrakis(N' '-(2-hydroxoethyl)-2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane, 5,6-Me(2)-HPTB = N,N,N',N'-tetrakis(5,6-dimethyl-2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane). The molecular structures of 2-6 were established by single-crystal X-ray crystallography. Iron(II) complexes with ligands similar to the dinucleating ligands described herein have been used previously as model compounds for the dioxygen uptake at the active sites of non-heme iron enzymes. The same metastable (mu-peroxo)diiron(III) adducts were observed during these studies. They can be prepared by adding hydrogen peroxide to the iron(III) compounds 1-6. Using stopped-flow techniques these reactions were kinetically investigated in different solvents and a mechanism was postulated.
Westerheide
L
L
Institut für Anorganische Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany.
Müller
F K
FK
Than
R
R
Krebs
B
B
Dietrich
J
J
Schindler
S
S
D018360:Crystallography, X-Ray; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D006861:Hydrogen Peroxide / Q000737:chemistry* / Q000378:metabolism; D007700:Kinetics; D008024:Ligands; D015394:Molecular Structure; D010105:Oxygenases / Q000737:chemistry / Q000378:metabolism; D012997:Solvents
D005290:Ferric Compounds; D008024:Ligands; D012997:Solvents; D006861:Hydrogen Peroxide; D010105:Oxygenases; C021555:methane monooxygenase