Iron, Carbonyl

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. 

In addition to benzene and naphthalene derivatives, heteroaromatic compounds such as ferrocene[232, furan, thiophene, selenophene[233,234], and cyclobutadiene iron carbonyl complexpSS] react with alkenes to give vinyl heterocydes. The ease of the reaction of styrene with sub.stituted benzenes to give stilbene derivatives 260 increases in the order benzene < naphthalene < ferrocene < furan. The effect of substituents in this reaction is similar to that in the electrophilic aromatic substitution reactions[236]. 

Reactions of acetylene and iron carbonyls can yield benzene derivatives, quinones, cyclopentadienes, and a variety of heterocycHc compounds. The cyclization reaction is useful for preparing substituted benzenes. The reaction of / fZ-butylacetylene in the presence of Co2(CO)g as the catalyst yields l,2,4-tri-/ f2 butylbenzene (142). The reaction of Fe(CO) and diphenylacetylene yields no less than seven different species. A cyclobutadiene derivative [31811 -56-0] is the most important (143—145). 

Exposure to metal carbonyls can present a serious health threat. Nickel carbonyl is considered to be one of the most poisonous inorganic compounds. However, the toxicological information available on metal carbonyls is restricted to the mote common, commercially important compounds such as Ni(CO)4 and Ee(CO). Other metal carbonyls are considered potentially dangerous, especially ia the gaseous state, by analogy to nickel and iron carbonyls. Data concerning toxicological studies on a few common metal carbonyls are Hsted ia Table 6 (185). Additional toxicity data are OSHA personal exposure limits (PEL) for Ee(CO) this is 8 h at 0.1 ppm, whereas for the much more toxic Ni(CO)4 it is 8 h at 0.001 ppm, with a toxic concentration TCLq low (of 7 mg/m ) for human inhalation. 

Pyridazines form complexes with iodine, iodine monochloride, bromine, nickel(II) ethyl xanthate, iron carbonyls, iron carbonyl and triphenylphosphine, boron trihalides, silver salts, mercury(I) salts, iridium and ruthenium salts, chromium carbonyl and transition metals, and pentammine complexes of osmium(II) and osmium(III) (79ACS(A)125). Pyridazine N- oxide and its methyl and phenyl substituted derivatives form copper complexes (78TL1979). 

There appear to be few examples of the formation of azetidin-2-ones by closure of the C(2) —C(3) bond. One reaction which fits into this category involves reaction of the iron carbonyl lactone complexes (144) with an amine to give the allyl complexes (145) which on oxidation are converted in high yield to 3-vinyl-/3-lactams (146) (80CC297). 

The methods of preparation of ferrocene have been reviewed by Pauson and by Fischer. Ferrocene has been made by the reaction of ferric chloride with cyclopentadienylmagnesium bromide, by the direct thermal reaction of cyclopentadiene with iron metal, by the direct interaction of cyclopentadiene with iron carbonyl, by the reaction of ferrous chloride with cyclopentadiene in the presence of organic bases such as diethyl-amine, by the reaction of ferrous chloride with sodium cyclo-[lentadienide in liquid ammonia, and from cyclopentadiene and... 

The carbon black studied here was prepared by a CO2 laser-driven pyrolysis of a mixture of benzene, ethylene, and iron carbonyl[34]. As synthesized, TEM... 

The double bond migration in steroid hydrocarbons catalyzed by acids or noble metals (see, for example, ref. 185) will not be discussed here. A general review of nonsteroid olefin isomerization has recently been published. Iron carbonyl has been used to isomerize steroidal dienes. 

The treatment of iron carbonyls with aqueous or alcoholic alkali can, by varying the conditions, be used to produce a series of interconvertible carbonylate anions [HFe(CO)4] , [Fe(CO)4] ", [Fe2(CO)g]2-, [HFe3(CO) ]- and [Fe4(CO)i3]"". Of these the first has a distorted trigonal bipyrarmdal stracture with axial H, the second... 

Direct substitution of the carbonyls themselves is of course possible. Besides Group 15 donor ligands, unsaturated hydrocarbons give especially interesting products. The iron carbonyl acetylenes provided early examples of the use of carbonyls in organic synthesis. From them a wide variety... 

The chemistry of l-rerr-butyl-3,4-dimethylphosphole toward iron carbonyls differs in some respects (81IC2848). Thus, with Fc3(CO)l2, complexes containing the... 

Fe—Fe bond can be assigned structures 201 or 202 based on spectral data. The other product of this reaction is 193 (R = r-Bu), however, it is produced in minor amounts. Complexes 199 (R = R = r-Bu, R = Ph, R = r-Bu) were obtained. Reaction of 146 (M = Mo, R = Ph, R = R = Ft, R = r" = Me) with (benzyli-deneacetone)iron carbonyl gives rise to the bimetallic complex 200 (M = Mo), which reacts further with the free phosphole to form the bimetallic heteronuclear sandwich 203. The preferable coordination of the molybdenum atom to the dienic system of the second phosphole nucleus is rather unusual. The molybdenum atom is believed to have a greater tendency to coordinate via the trivalent phosphorus atom than via the dienic system. 

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