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Iron complexes, with olefin

Scheme 4-122. Cyclization of (ri -diene)iron complexes with olefins. Scheme 4-122. Cyclization of (ri -diene)iron complexes with olefins.
Iron hydride complexes can be synthesized by many routes. Some typical methods are listed in Scheme 2. Protonation of an anionic iron complex or substitution of hydride for one electron donor ligands, such as halides, affords hydride complexes. NaBH4 and L1A1H4 are generally used as the hydride source for the latter transformation. Oxidative addition of H2 and E-H to a low valent and unsaturated iron complex gives a hydride complex. Furthermore, p-hydride abstraction from an alkyl iron complex affords a hydride complex with olefin coordination. The last two reactions are frequently involved in catalytic cycles. [Pg.29]

The reactions of metal-carbene complexes with olefins are important in catalysis and organic synthesis. The first reaction disclosed by Pettit in 1966 involved transient [FeCp(CO)2(=CH2)] that reacted with styrene to give phenylcyclopropane resulting from methylene transfer from the metallacarbocation to the olefin, a reaction that was shown later to be general with iron-methylene complexes of this series. ... [Pg.212]

Intermediate Ti -dienyliumiron complexes which are formed by reaction of (Ti -a-hydroxy-l,3-diene)iron complexes with boron trifluoride etherate can also be trapped by olefins. An intramolecular variation with tethered olefins leads to a stereospecific cyclization. The resulting cyclohexyl cations can be stabilized by addition of nucleophiles... [Pg.669]

Alkenes in (alkene)dicarbonyl(T -cyclopentadienyl)iron(l+) cations react with carbon nucleophiles to form new C —C bonds (M. Rosenblum, 1974 A.J. Pearson, 1987). Tricarbon-yi(ri -cycIohexadienyI)iron(l-h) cations, prepared from the T] -l,3-cyclohexadiene complexes by hydride abstraction with tritylium cations, react similarly to give 5-substituted 1,3-cyclo-hexadienes, and neutral tricarbonyl(n -l,3-cyciohexadiene)iron complexes can be coupled with olefins by hydrogen transfer at > 140°C. These reactions proceed regio- and stereospecifically in the successive cyanide addition and spirocyclization at an optically pure N-allyl-N-phenyl-1,3-cyclohexadiene-l-carboxamide iron complex (A.J. Pearson, 1989). [Pg.44]

The following compounds have been obtained from thiete 1,1-dioxide Substituted cycloheptatrienes, benzyl o-toluenethiosulfinate, pyrazoles, - naphthothiete 1,1-dioxides, and 3-subst1tuted thietane 1,1-dioxides.It is a dienophile in Diels-Alder reactions and undergoes cycloadditions with enamines, dienamines, and ynamines. Thiete 1,1-dioxide is a source of the novel intermediate, vinylsulfene (CH2=CHCH=SQ2). which undergoes cyclo-additions to strained olefinic double bonds, reacts with phenol to give allyl sulfonate derivatives or cyclizes unimolecularly to give an unsaturated sultene. - Platinum and iron complexes of thiete 1,1-dioxide have been reported. [Pg.215]

The corresponding iron-catalyzed oligomerization of ethylene was developed by Gibson and coworkers [125]. A combination of an iron precatalyst with MAO (methyl aluminoxane) yields a catalyst that affords ethylene oligomers (>99% linear ot-olefin mixtures). The activity of ketimine iron complexes (R = Me) is higher than that of the aldimine analogs (R = H) and also the a-value of the oligomer is better (Scheme 41). [Pg.58]

A few further general examples of zinc catalytic activity or reactivity include the following. Other zinc-containing systems include a zinc phenoxide/nickel(0) catalytic system that can be used to carry out the chemo- and regioselective cyclotrimerization of monoynes.934 Zinc homoenolates have been used as novel nucleophiles in acylation and addition reactions and shown to have general utility.935,936 Iron/zinc species have been used in the oxidation of hydrocarbons, and the selectivity and conditions examined.362 There are implications for the mechanism of metal-catalyzed iodosylbenzene reactions with olefins from the observation that zinc triflate and a dizinc complex catalyze these reactions.937... [Pg.1231]

Traditionally, iron-based catalysts have been used for FT synthesis when the syngas is coal derived, because of their activity in both FTS and WGS reactions. Complex mixtures of straight-chain paraffins, olefins, and oxygenate (in substantial proportions) compounds are known to be formed during iron-based FTS. Olefin selectivity of iron catalysts is typically greater than 50% of the hydrocarbon products at low carbon numbers, and more than 60% of the produced olefins are a-olefins.13 For iron-based catalysts, the olefin selectivity decreases asymptotically with increasing carbon number. [Pg.281]

In marked contrast to the results of Gassman and Schrock, major differences were noted by Casey and co-workers in a series of studies utilizing phenylcarbene-substituted W(0) complexes in reactions with olefins. The H NMR spectra of new phenylcarbene tungsten and iron (69) complexes indicate a substantial positive charge residing on the carbene carbon, and as expected, these complexes readily form ylides on reaction with phosphines ... [Pg.463]

Better results for the porphyrin complex-catalyzed asymmetric epoxidation of prochiral olefins were achieved by Naruta et al.98 using iron complexes of chiral binaphthalene or bitetralin-linked porphyrin 128 as chiral catalysts. As shown in Scheme 4-45, asymmetric epoxidation of styrene or its analogs provided the product with good ee. Even better results were obtained with substrates bearing electron-withdrawing substituents. [Pg.243]

The key feature of efficient metathesis catalysts seems to be their ability to form, before the [2 + 2] cycloaddition step, a n complex with the alkene (Figure 1.7). Comparison of catalyst 1 with the iron complex 3 shows that the latter, although cationic, will not be able to bind to an olefin, because this would give rise to a complex with 20 valence electrons. A similar argument can be used... [Pg.6]

Although the reaction responsible for the generation of the hydride is not specified, it is assumed that it arises from a disproportionation of iron carbonyl complexes. The hydride presumably adds after ir-complexing to form the c-bonded complex which then splits out the metal hydride in either direction. The ir-complexed olefin may then be displaced by another olefin or undergo another hydride addition-elimination sequence. The second path involves olefin complexing with the deficient Fe(CO)3 species and formation of a jr-allyliron hydride intermediate ... [Pg.30]

The first metal-olefin complex was reported in 1827 by Zeise, but, until a few years ago, only palladium(II), platinum(Il), copper(I), silver(I), and mercury(II) were known to form such complexes (67, 188) and the nature of the bonding was not satisfactorily explained until 1951. However, recent work has shown that complexes of unsaturated hydrocarbons with metals of the vanadium, chromium, manganese, iron, and cobalt subgroups can be prepared when the metals are stabilized in a low-valent state by ligands such as carbon monoxide and the cyclopentadienyl anion. The wide variety of hydrocarbons which form complexes includes olefins, conjugated and nonconjugated polyolefins, cyclic polyolefins, and acetylenes. [Pg.78]

Olefins readily displace CO groups from the iron carbonyls, Fe(CO)5, Fe2(CO)9, and Fe3(CO)12, to form complexes in which a C C bond of the olefin takes the place of each displaced CO group, and by donating its ir-electrons preserves the formal inert gas electron configuration of the iron atom in the complex. Acrylonitrile is the only reported example of a monoolefin complexing with iron in this way, but many complexes of iron with polyolefins are known. [Pg.85]

The ease with which olefins form complexes with metals naturally led to investigation of acetylenes as ligands but until recent years only a few ill-defined, unstable acetylene complexes of copper and silver were known. Now complexes of acetylenes with metals of the chromium, manganese, iron, cobalt, nickel, and copper subgroups are known. These complexes fall naturally into two classes—those in which the structure of the acetylene is essentially retained and those in which the acetylene is changed into another ligand during complex formation. Complexes of the first class are discussed here and the second class is discussed in Section VI. [Pg.103]

Both conjugated and nonconjugated olefins form complexes with the transition-metal carbonyls. Despite the fact that the first known complex, Zeises salt K(PtC2H4Cl3), discovered in 1827, was that of a simple olefin, complexes of monoolefins are rather limited in number. However, nonconjugated diolefins (L) react with group-VI carbonyls to form complexes of the type LM(CO)4 an example is provided by tetracarbonyl-bicyclo-(2,2, l)hepta-2,5-diene chromium (2) (Fig. 1). In contrast, the iron carbonyls... [Pg.2]


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Complexes with olefins

Iron complexes olefin

Iron complexes, with

Iron olefin

Olefin complexation

Olefin complexes

Olefines, complexes

With Olefins

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