Iron complexes oxidative dimerization

In model studies involving Fe(n) species, three broad approaches have been used to mitigate the problem of autoxidation of the iron (Hay, 1984). These are (i) the use of low temperatures so that the rate of oxidation becomes very slow (ii) the synthesis of ligands containing steric barriers such that dimerization of the iron complex is inhibited, and (iii) immobilization of the iron complex on a solid surface such that dimerization once again will not be possible. 

It is essential to characterize the reactant species in solution. One of the problems, for example, in interpreting the rate law for oxidation by Ce(IV) or Co(III) arises from the difficulties in characterizing these species in aqueous solution, particularly the extent of formation of hydroxy or polymeric species. We used the catalyzed decomposition of HjOj by an Fe(III) macrocycle as an example of the initial rate approach (Sec. 1.2.1). With certain conditions, the iron complex dimerizes and this would have to be allowed for, since it transpires that the dimer is catalytically inactive. In a different approach, the problems of limited solubility, dimerization and aging of iron(III) and (Il)-hemin in aqueous solution can be avoided by intercalating the porphyrin in a micelle. Kinetic study is then eased. 

The oxidation of [Cr(SH)(H20)5]2+ by I2 or Fe3+ under aerobic conditions in acid solutions gives the disulfido-bridged complexes [(H20)5CrS2Cr(H20)5]4+ and [(H20)sCr(S2H)Fe-(H20)5]4+ respectively (Scheme 100).967,968 The latter complex can also be obtained by substitution of chromium(III) in the former complex by iron(II) under acid conditions. The product distribution in the iron(UI) oxidation of [Cr(SH)(H20)5]2+ is pH dependent and at 298 K, pH = 1 the heteronuclear dimer [(H20)5Cr(S2H)Fe(H20)5]4+ constitutes over 80% of the product mixture. The rate of this reaction shows a [H+] 1 dependence, an observation consistent with [CrS(H20)5]+ being the kinetically active species. 

Cyclohexene oxidation in the presence of the molybdenum complex, [C5Hr)Mo(CO)3]2, gave two major products at low conversion VI and VII nearly 1 1 mole ratio, Table V. The ketone, VIII, was formed in very low yield in contrast to oxidations using the iron complex. This reaction is far more selective than the oxidation of cyclohexene in the presence of Mo02(acac)2 reported by Gould and Rado (24). When a cyclohexene solution of V was exposed to [CsHsMk COJs] at 70°C, VI and VII were formed in approximately equimolar amounts (Table VI). These data show that the molybdenum complex efficiently catalyzes the epoxidation of cyclohexene by V before the allylic hydroperoxide decomposes substantially. Reaction 16 represents the predominant course of cyclohexene oxidation in the presence of cyclopentadienyltricarbonyl molybdenum dimer. 

Nitric Oxide Halide Complexes. The dimeric diamagnetic halides [Fe(NO)2X]2 have essentially tetrahedrally coordinated iron atoms with bridging halides. The trinitrosyl halides [Fe(NO)3X] are comparatively much less stable they can be prepared by the reaction of [Fe(CO)2X]2 with iron and nitric oxide. The complexes [Fe(NO)X3] and [Fe(NO)2X2] are known but much more work has been done on the reactivity of the dimeric dinitrosyl, and some of its reactions are illustrated in Scheme 2. 

Treatment of 2,2,4,4-tetramethyl-3-thietanone with diiron nonacarbonyl gives the binuclear iron complex 381. 2,2-Dimethyl-3-thietanone undergoes oxidative dimerization to 382 on treatment with potassium ferricyanide. Methylene-3-thietanones such as 359 add chlorine from thionyl chloride to the carbon-carbon double bond. 2,2,4,4-tetramethyl-3-thietanone is converted to the 3-thione in 14% yield by treatment with hydrogen sulfide-hydrogen chloride. Electrochemical reduction of the thione produces radical anions. 

Oxidation of tri-terr-butylcyclobutadiene(tricarbonyl)iron complex with ammonium ce-rium(IV) nitrate or iron(III) nitrate in acetone did not afford the expected dimer of ix i-tert-butylcyclobutadiene, but gave exclusively l,2-di-ter/-butyl-3-(2,2-dimethyl)propanoylcyclo-propene (4), in quantitative yield. ... 

While peroxo dimer formation is sometimes reversible for cobalt complexes, it inevitably leads to further oxidations in case of iron complexes. Steric hindrance about the metal center would prevent dimerization processes. 

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