Iron photochemical reactions

We cover each of these types of examples in separate chapters of this book, but there is a clear connection as well. In all of these examples, the main factor that maintains thermodynamic disequilibrium is the living biosphere. Without the biosphere, some abiotic photochemical reactions would proceed, as would reactions associated with volcanism. But without the continuous production of oxygen in photosynthesis, various oxidation processes (e.g., with reduced organic matter at the Earth s surface, reduced sulfur or iron compounds in rocks and sediments) would consume free O2 and move the atmosphere towards thermodynamic equilibrium. The present-day chemical functioning of the planet is thus intimately tied to the biosphere. 

Transition-metal catalyzed photochemical reactions for hydrogen generation from water have recently been investigated in detail. The reaction system is composed of three major components such as a photosensitizer (PS), a water reduction catalyst (WRC), and a sacrificial reagent (SR). Although noble-metal complexes as WRC have been used [214—230], examples for iron complexes are quite rare. It is well known that a hydride as well as a dihydrogen (or dihydride) complex plays important roles in this reaction. 

Iron oxides in the finely divided form have the power to promote (catalyse) a range of redox and photochemical reactions (Tab. 11.7). The preliminary step is the adsorption of the reacting species on the iron oxide. This may be followed either by direct reaction with the Fe surface atoms or surface functional groups or the surface may promote reaction between the adsorbed species and a solution species such as dissolved oxygen. 

Hoigne, J., Y. Zuo, and L. Nowell, Photochemical Reactions in Atmospheric Waters Role of Dissolved Iron Species, in Aquatic and Surface Photochemistry (G. Helz, R. Zepp, and D. Crosby, Eds.), Chap. 4, pp. 75-84, Lewis, Boca Raton, FL, 1994. 

No COT analogues of 64 or 65 are known in iron chemistry, but the photochemical reaction of [Os3(CO)12] with COT has been reported to yield the osmium(II) complex 66, which rearranges to the thermodynamically stable... 

A rare example of a ferracycloheptane 108 was obtained as the product of the photochemical reaction of a Petitt s cyclobutadiene iron complex with dimethyl-maleate [Eq. (43)].118 The ferracycloheptane arises from the insertion of a maleate into each of two Fe-C bonds and might therefore be considered a special case of alkene trimerisation (vide infra). The cyclobutene fragment in the final metallacycle remains coordinated to iron, as established crystallographically (Fig. 34). 

A basic understanding of the electronic structures of iron bearing clays and oxides is needed before one can understand the mechanisms of electron transfer and photochemical reactions associated with these minerals. This chapter will discuss the electronic structures of iron bearing clays and oxides (primarily from cluster molecular orbital calculations) and compare theoretical results with experiment. The discussion will be... 

Sun Y, Pignatello JJ. Photochemical reactions involved in the total mineralization of 2,4-D by iron(3 +)/hydrogen peroxide/UV. Environ Sci Technol 1993 27 304-310. 

Like most photochemical reactions, benzylic fragmentation has been known from the beginning of the twentieth century. The photoinduced cleavage of triphenylmethylcarbinol has been noted by Gomberg in Ann Arbor in 1913 [1] and the generation of triarylmethyl cationic dyes from their leuco form by Lifschitz in Zurich in 1919 [2]. A solution of the colorless derivative obtained from p-rosaniline and cyanide became colored in a few seconds when exposed to an iron arc lamp (Sch. 1, old and new notation). 

Sun, Y. and Pignatello, J.J. (1993) Photochemical reactions involved in the total mineralization of 2,4-D by iron(3+)/hydrogen peroxide/UV. Environ. Sci. Technol. 27, 304-310 Toepfer, B., Gora, A. and Li Puma, G. (2006) Photocatalytic oxidation of multicomponent solutions of herbicides Reaction kinetics analysis with explicit photon absorption effects. Appl. Catal. B Environ. 68,171-180... 

Many common metallic impurities in paper, particularly compounds of some of the transition metals, contribute to degradation of cellulose by hydrolytic or oxidative reactions. The more important in commercial papers are iron and copper compounds, whereas some others such as magnesium compounds have been observed to exert protective effects (7). It is clearly desirable that the content of undesired metallic ions be kept low in permanent papers. Titanium dioxide, commonly used as a filler, has been observed to promote degradation by photochemical reactions. The predictive potential of metallic content in relation to permanence, however, does not allow the setting of permissible limits at the present time. 

We have reported here the preparations and treatment conditions that are needed to reduce Iron Ions to metallic Iron In zeolites. Although we have not Isolated highly-dis-spersed superparamagnetic Iron particles In zeolites, we have shown that these iron-containing zeolites are active catalysts in Fischer-Tropsch and in olefin isomerization reactions. The added insight that stems from the use of in-situ Mossbauer experiments has led to the preparation of new active catalysts that can be selectively activated. We presently are studying photochemical reactions of other metal carbonyl complexes in zeolites and believe that increased selectivity is a major benefit in these types of reaction. 

Fig. 8 Molecular orbital depiction of the concept of band-gap energies with corresponding molecular orbital transitions for the Fe(III) oxyhydroxides. The photon action spectra [134,230] for photochemical reactions [136,141,143] of the iron oxyhydroxides (i.e., a-Fe2C>3, a-FeOOH, /S-FeOOH and y-FeOOH) indicate that the most effective electron transition leading to photocatalysis or photoreduction is the O2- to Fe3+ transition shown schematically above...

Fig. 12 Schematic representation of the photochemical reaction of Fe(III)-aquachelin complexes. The dashed line indicates the position of photolytic cleavage of the aquachelin ligand. Iron(III) is reduced to iron(II) via ligand-to-metal charge transfer (Orn = ornithine) (From [75])...

Iron(III) halides are obtained by direct halogenation of Fe but FeBr3 and Fel3 are best prepared by a photochemical reaction 4... 

A variety of synthetic routes to monoene and polyene tri-fluorophosphine-transition metal complexes have been devised. Direct photochemically induced reaction of a metal-PF3 complex with an activated alkene or diene (method A) has proved useful only for iron, the products being either [Fe(PF3)4(alkene)J or [Fe(PF3)3(diene)] (194). Mixed carbonyl-trifluorophosphine complexes of the type [Fe(PF3)x(CO)3 x(diene)] result from either thermal or photochemical reactions of dieneiron carbonyl complexes and PF3 (52, 53) (method B). The compounds are fluxional. 

PFe = O. Typical photochemical reactions of iron and other metalloporphyrins have been summarized by Suslick and Watson. ... 

Diene iron tricarbonyl complexes are prepared by thermal or photochemical reaction of conjugated dienes with iron pen-tacarbonyl in the presence of TMANO, triiron dodecacarbonyl, ()]" -benzylidenacetone)iron tricarbonyl, diiron nonacarbonyl, or diiron nonacarbonyl absorbed on silica gel in the absence of solvent. The latter method is particnlarly usefiil for the preparation of complexes from polar electron-rich dienes and heterodienes. A reductive complexation of cycloheptatrienes using iron tricarbonyl and sodium borohydride to give cyclo-heptadiene iron tricarbonyl has been developed (Scheme 126). 

Figure 1. Photochemical reactions of iron-substituted pentaborane clusters.10...

There has been recent interest in a somewhat different aspect of adsorption and reaction on metal oxides photocatalysis. The interest stems partially from that role that some transition-metal oxides can play in photochemical reactions in the atmosphere. Atmospheric aerosol particles can act as substrates to catalyze heterogeneous photochemical reactions in the troposphere. Most tropospheric aerosols are silicates, aluminosilicates and salts whose bandgaps are larger than the cutoff of solar radiation in the troposphere (about 4.3 eV) they are thus unable to participate directly in photoexcited reactions. However, transition-metal oxides that have much smaller bandgaps also occur as aerosols — the most prevalent ones are the oxides of iron and manganese — and these materials may thus undergo charge-transfer excitations (discussed above) in the pres-... 

Photoinduced electron-transfer in the opposite direction was demonstrated upon irradiation of the Ru(bpy)3 +-Mb system in the presence of Co +(NH3)5Cl as a sacrificial electron acceptor (Figure 44B) [244]. The photochemical reaction results in the formation of ferryl species (i.e., Fe(IV)-heme), with the intermediate formation of the porphyrin cation radical (as demonstrated using laser flash photolysis [237]). The electron-transfer cascade includes the primary oxidative quenching of the excited chromophore, Ru(bpy)3"+, by Co +(NH3)5Cl to yield Ru(bpy)3 + [E° = +1.01 V vs. SCE). The resulting oxidant efficiently takes an electron from the porphyrin ring (fcet = 8.5 x 10 s ) and the porphyrin cation radical produced further oxidizes the central iron atom, converting it from the Fe(III) state to the Fe(IV) state (/cet = 4.0 x 10 s at pH 7.5). 

Studies have been made of the photochemical reactions of vinyloxiranes with iron carbonyl. The four diastereoisomers of 2,4-hexadienemonooxirane take part in photochemical reactions that are stereospecific. The structure of the iron complex has been determined by x-ray crystallography. Complexes formed from dienemonooxiranes with iron carbonyl can be oxidized to lactones. ... 

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