Pentacarbonyl, iron, reaction with

Other Reactions. Due to the highly reactive conjugated double bonds, butadiene can undergo many reactions with transition metals to form organometaHic complexes. For instance, iron pentacarbonyl reacts with butadiene to produce the tricarbonyl iron complex (10) (226). This and many other organometaHic complexes have been covered (227). 

Various substituted silacyclopentadienes react with iron or cobalt carbonyl compounds to give stable i 4-silacyclopentadiene complexes. Thus, with iron pentacarbonyl, reaction occurs at 150°-200° in an autoclave, with Fe2(CO)9 at 40°-60°, and with Fe3(CO)12 at 80° (20, 21, 49, 132) the same complex can be obtained from a dibromosilacyclopen-tene and diiron nonacarbonyl, under mild conditions (19) ... 

It is deduced from infrared data (206) that iron pentacarbonyl reacts with bromine at — 80° C to form the cationic halogeno carbonyl [Fe(CO)sBr]+Br (206), and the covalent Br—CO—Fe(CO)4Br. From similar infrared data, however, it is concluded that the product is a seven-coordinate non-ionic complex Fe(CO)5Br2 (76) The reaction of Os(CO)3(PPh3)2 with hydrogen chloride produces a cationic hydrido carbonyl, which may be isolated, although it readily reverts to a neutral dichloride by attack of the associated chloride anion (52). 

Another reaction sequence encountered in metal carbodiimide interactions occurs in the reaction of iron pentacarbonyl 40 with dialkylcarbodiimides, resulting in the formation of dehydroguanidino iron carbonyl complexes 41. ... 

The photochemical reaction of Group VI metal hexacarbonyls with mono-enes was studied several years ago, but only recently has the reaction of one of the hexacarbonyls, W(CO)s in fact, with conjugated dienes been investigated. The W(CO)6 proves to be an effective catalyst for cis trans isomerization of such dienes compounds of the type W(CO)6(diene), which must act as intermediates in such isomerizations, have been isolated and their reactions studied. Under normal conditions iron pentacarbonyl reacts with acetylene to produce a complicated mixture of products, but under irradiation in an argon matrix at — 256 °C the product is but-l-en-3-yne, complexed to the iron through the carbon-carbon triple bond only. This iron-alkyne-carbonyl compound is presumably an intermediate in the reaction under normal thermal conditions. In an argon matrix at — 256 C, iron pentacarbonyl reacts with ethylene to give Fe(CO)4(QH4). ... 

Condensation of vinyl chloride with formaldehyde and HCl (Prins reaction) yields 3,3-dichloro-l-propanol [83682-72-8] and 2,3-dichloro-l-propanol [616-23-9]. The 1,1-addition of chloroform [67-66-3] as well as the addition of other polyhalogen compounds to vinyl chloride are cataly2ed by transition-metal complexes (58). In the presence of iron pentacarbonyl [13463-40-6] both bromoform [75-25-2] CHBr, and iodoform [75-47-8] CHl, add to vinyl chloride (59,60). Other useful products of vinyl chloride addition reactions include 2,2-di luoro-4-chloro-l,3-dioxolane [162970-83-4] (61), 2-chloro-l-propanol [78-89-7] (62), 2-chloropropionaldehyde [683-50-1] (63), 4-nitrophenyl-p,p-dichloroethyl ketone [31689-13-1] (64), and p,p-dichloroethyl phenyl sulfone [3123-10-2] (65). 

Interaction of pentaphenylphosphole with iron pentacarbonyl gives rise to the tiVp) complex 190 [61JA4406 77JOM( 136)241 79ICA(35)231]. On the other hand, reaction of Ec3(CO)l2 leads to the formation of the V complex 191 and... 

Mesitaldehyde may be prepared from mesitylmagnesium bromide by the reaction with orthoformate esters3 or ethoxy-methyleneaniline 3 from acetylmesitylene by oxidation with potassium permanganate,4 from mesitoyl chloride by reduction,5 from mesityllithium by the reaction with iron pentacarbonyl and from mesitylene by treatment with formyl fluoride and boron trifluoride,7 by treatment with carbon monoxide, hydrogen chloride, and aluminum chloride,8 or by various applications of the Gatterman synthesis.9-11... 

Iron pentacarbonyl has been shown to be a catalyst for the reaction of organic azides with isocyanides, giving carbodiimides 127) [Eq. (21)]. 

The low-valent ferrate [Fe(CO)3(NO)] 76 or Hieber anion was discovered some 50 years ago by Hieber and Beutner [43, 44] in order to extend the Hieber base reaction [45,46], in which iron pentacarbonyl 78 reacts with alkaline bases to form the [Fe(CO)4] anion [47, 48]. Compared to its homoleptic analogue, the Hieber anion is more stable because the electron-withdrawing character of the nitrosyl ligand stabilizes the negative charge at the iron atom. 

Allyl groups attached directly to amine or amide nitrogen can be removed by isomerization and hydrolysis.228 These reactions are analogous to those used to cleave allylic ethers (see p. 266). Catalysts that have been found to be effective include Wilkinson s catalyst,229 other rhodium catalysts,230 and iron pentacarbonyl.45 Treatment of /V-allyl amines with Pd(PPh3)4 and (V,(V -dimethylbarbi Lurie acid also cleaves the allyl group.231... 

The preparation of carbonylmetals by treating a transition metal halide either with carbon monoxide and zinc, or with iron pentacarbonyl is well-known and smooth. However, a violent eruptive reaction occurs if a methanolic solution of a cobalt halide, a rhodium halide or a ruthenium halide is treated with both zinc and iron pentacarbonyl. 

Pyrazoles can be synthesized by thermal cycloreversion of adducts formed in the 1,3-dipolar cycloaddition of alkyldiazoacetates with norbornadiene. The rate of the primary process of cycloaddition is accelerated by iron pentacarbonyl (Scheme 88)155 a similar catalytic effect has been observed during the formation of ethyl 5-phenyl-A2-pyrazoline-3-carboxylate from cycloaddition of ethyl diazoacetate and styrene.155 Reactions of this type are catalyzed presumably because of coordination of one or both reactants to the transition metal, and a wider study of the effect of a variety of complexes on 1,3-dipolar cycloaddition processes would be valuable. 

The formation of l,3,4-triarylpyrroline-2,5-diones from the reaction of diphenylcyclopropenone and N-sulfinylarylamines with nickel carbonyl has been described earlier (see Scheme 36 in Section IV,A,2).64 In contrast with this result, 2,4,5-triphenyl-3-isothiazolone 1-oxide is produced in this type of process using iron pentacarbonyl, and the analogous cyclohexyl derivative is formed in a nickel carbonyl-mediated reaction (Scheme 115).64 It is probable that metallocyclic species (cf. 93) are intermediates in these transformations. 

In this section, we start by describing the main features of the photolytic chemistry of iron pentacarbonyl and related species, focusing on the experimental data. We then describe our and other people s computational work aimed at understanding the reactivity of the fragments formed upon photolysis, with a focus on the spin-forbidden steps. We consider, in turn, the addition of ligands to Fe(CO)4, Fe(CO)3, and Fe(CO)3L (where L is a ligand such as H2 or ethene). For some of the reactions, we include some new computational results as well as a review of existing work. 

---