Iron clusters methane

Methylococcus capsulatus, methane monooxygenase, diferric iron cluster, 43 362-363 2-(l-Methylpyridinium-4-yl)-4,4,5,5,-... 

The role of iron clusters in Fischer-Tropsch catalysis has been the focus of considerable studies. Cagnoli et al. have recently studied the role of Fe clusters on silica and alumina supports for methanation.22 Chemisorption, catalysis and Mossbauer spectroscopy experiments were used to study the effect of dispersion and the role of various supports. Although several oxidation states of iron were observed, the focus of this research was on Fe clusters which were found to be on the order of 12 A crystal size. The authors proposed that metal support interactions were greater for silica than alumina supports and that selectivity differences between these catalysts were due to differences in surface properties of silica vs. alumina. Differences in selectivity for Fe/SiC>2 catalysts at different H2/CO ratios were attributed to differences in coadsorption of H2 and CO. Selectivity differences are difficult to explain in such systems even when only one metal is present. 

Shriver could show that oxyjten proionation of an iron cluster with MjSOsCFs gave methane (Equation (44)) ( 4). 

FIGURE 8. Postulated mechanism for MMO. The inner cycle are postulated intermediates in the catalytic cycle (only the binuclear iron cluster of the MMOH component is shown). The outer cycle represents the intermediates detected during a single turnover beginning with diferrous MMOH and ending with diferric MMOH. The rate constants shown are for 4 C and pH 7.7. The rate shown for the substrate reaction RH with Q is that for methane. The alignment of the two cycles shows the postulated structures for the intermediates. 

Davydov, A., Davydov, R., Gr%oslund, A., Lipscomb, J. D., and Andersson, K. K., 1997, Radiolytic reduction of methane monooxygenase dinuclear iron cluster At 77K6EPR evidence for conformational change upon reduction or binding of component B to the diferric state, J. Biol. Chem. 272 702267026. 

Fox, B. G., Surerus, K. K., M,nck, E., and Lipscomb, J. D., 1988, Evidence for a p-oxo-bridged binuclear iron cluster in Oie hych oxylase component of methane monooxygenase. MYs-bauer and EPR studies, J. Biol. Chem. 263 10553nl0556. 

Transition metal catalysts, specifically those composed of iron nanoparticles, are widely employed in industrial chemical production and pollution abatement applications [67], Iron also plays a cracial role in many important biological processes. Iron oxides are economical alternatives to more costly catalysts and show activity for the oxidation of methane [68], conversion of carbon monoxide to carbon dioxide [58], and the transformation of various hydrocarbons [69,70]. In addition, iron oxides have good catalytic lifetimes and are resistant to high concentrations of moisture and CO which often poison other catalysts [71]. Li et al. have observed that nanosized iron oxides are highly active for CO oxidation at low tanperatures [58]. Iron is unique and more active than other catalyst and support materials because it is easily reduced and provides a large number of potential active sites because of its highly disordered and defect rich structure [72, 73]. Previous gas-phase smdies of cationic iron clusters have included determination of the thermochemistry and bond energies of iron cluster oxides and iron carbonyl complexes by Armentrout and co-workers [74, 75], and a classification of the dissociation patterns of small iron oxide cluster cations by Schwarz et al. [76]. 

Fig. 2. Diferric iron clusters from ribonucleotide reductase R2 subunit and methane monooxygenase hydroxylase. The drawings are based on (18, 19) for RNR-R2 and (15) for MMOH.

Fig. 1. Diferric iron clusters form hemer3fthrin, ribonucleotide reductase R2 subunit, and methane monooxygenase hydroxylase. The figure was made with the RasMol 2.0 program, and the protein coordinates as PDB files were obtained from Brookhaven Protein Data Bank. Only the amino acids (histidines, green carboxylates, black oxygen, red nitrogen, yellow acetate, blue iron, violet) coordinated to the iron cluster are shown, coordinated waters are not indicated. The first subunit containing the cluster is shown. Diferric Hr is from sipunculid worm Themiste dyscritra). The RNR-R2 is from E. coli. The MMOH is from Methvlococcus caosulatus (Bath).

The introduction of iron in the lattice of zeolite topologies such as MFI and CFI is performed via direct synthesis and post-synthetic modification. Dinuclear iron clusters in appropriate zeolites realize oxidation of methane into methanol at room temperature after N2O activation. Both mono and dinuclear iron coordination and lattice coordination is treated with theory and experiment. In FeCIT-5 and Fe-ZSM5 are made by over-exchange via sublimation of iron salts in Al-zeolites. When extra-framework iron oxides are made in zeolites, the extraframework iron oxide clusters can be anchored to zeolites. 

Covalent. Formed by most of the non-metals and transition metals. This class includes such diverse compounds as methane, CH4 and iron carbonyl hydride, H2Fe(CO)4. In many compounds the hydrogen atoms act as bridges. Where there are more than one hydride sites there is often hydrogen exchange between the sites. Hydrogens may be inside metal clusters. 

The multiprotein complex methane monooxygenase (MMO) serves meth-anotrophs to convert methane to methanol. It can be either soluble (sMMO) or membrane bound ( particulate , pMMO) and it typically consists of three components, a reductase (MMOR), a component termed protein B (MMOB) and a hydroxylase denoted MMOH. The nature of the metal cofactors in the latter component are reasonably well understood for sMMO as will be discussed in the non-heme iron section. For the pMMO of Methylococcus capsulatus an obligate requirement for copper was shown. As reported in reference 1 a trinuclear Cu(II) cluster was discussed128 but the number and coordination of coppers still is a matter of continuing investigation since then. 

The synthetic methods used involve reaction of a cluster anion with [AuCIL], elimination of methane between a cluster hydride and [AuMeL] or addition of LAu+ units to metal-metal bonds. The emphasis here will be on structure and reactions of the complexes. Some examples of mixed gold clusters are given in Table 15, where it can be seen that most work has been on derivatives of clusters of iron, ruthenium and osmium. 

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