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Oxidation by dioxygen of manganese(II) and iron(II) complexes.

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Title: Oxidation by dioxygen of manganese(II) and iron(II) complexes.
Authors: Belli Dell’Amico, Daniela1, Labella, Luca1 labella@dcci.unipi.it, Marchetti, Fabio1, Mastrorilli, Piero2,3, Samaritani, Simona1, Todisco, Stefano2,3
Source: Polyhedron. Nov2013, Vol. 65, p275-281. 7p.
Subjects: Manganese, Metal ions, Iron ions, Metal complexes, Dioxygenases, Oxidation
Abstract: Abstract: Fast oxidations of the iron(II) N,N-dialkylcarbamato complexes [Fe(II)(O2CNR2)2] n (R=Et, n =6, 1; R= i Pr, 2) and [Fe(II)8(μ4-O)2(O2CNiPr2)12], 3, by dioxygen were carried out both in an anhydrous hydrocarbon and in the solid state affording [Fe(III)2(O)(O2CNR2)4] x , 7 and 8 for R=Et and i Pr, respectively, and [Fe(III)4(O)3(O2CNiPr2)6] y , 9. The stoichiometric O2 uptake was not accompanied by oxidation of the ligand. Recovery of unchanged starting material was observed when the manganese(II) derivatives [Mn(II)(O2CNR2)2] n (R=Et, n =6, 4; R= i Pr, 5) were treated with O2. Nevertheless, when [Mn(II)8(μ4-O)2(O2CNiPr2)12], 6, prepared in situ by reaction of 5 with water (Mn/H2O molar ratio=4), was reacted with O2, complete oxidation occurred to a product where manganese showed an average oxidation number III, [Mn(III)4(O)3(O2CN i Pr2)6] y , 10. The product [Mn(II)6Mn(III)2(μ4-O)2(μ3-O)(O2CN i Pr2)12], 11, obtained by partial oxidation of 6 by O2, has been characterised by X-ray diffraction methods. [Copyright &y& Elsevier]
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Abstract:Abstract: Fast oxidations of the iron(II) N,N-dialkylcarbamato complexes [Fe(II)(O2CNR2)2] n (R=Et, n =6, 1; R= i Pr, 2) and [Fe(II)8(μ4-O)2(O2CNiPr2)12], 3, by dioxygen were carried out both in an anhydrous hydrocarbon and in the solid state affording [Fe(III)2(O)(O2CNR2)4] x , 7 and 8 for R=Et and i Pr, respectively, and [Fe(III)4(O)3(O2CNiPr2)6] y , 9. The stoichiometric O2 uptake was not accompanied by oxidation of the ligand. Recovery of unchanged starting material was observed when the manganese(II) derivatives [Mn(II)(O2CNR2)2] n (R=Et, n =6, 4; R= i Pr, 5) were treated with O2. Nevertheless, when [Mn(II)8(μ4-O)2(O2CNiPr2)12], 6, prepared in situ by reaction of 5 with water (Mn/H2O molar ratio=4), was reacted with O2, complete oxidation occurred to a product where manganese showed an average oxidation number III, [Mn(III)4(O)3(O2CN i Pr2)6] y , 10. The product [Mn(II)6Mn(III)2(μ4-O)2(μ3-O)(O2CN i Pr2)12], 11, obtained by partial oxidation of 6 by O2, has been characterised by X-ray diffraction methods. [Copyright &y& Elsevier]
ISSN:02775387
DOI:10.1016/j.poly.2013.08.011