The Reaction of the [CpFe(CO)2]− Anion with Pentafluorochlorobenzene: Nucleophilic Aromatic Substitution by Halogen-Metal Exchange

Artamkina, G. A.; Sazonov, P. K.; Ivushkin, V.A.; Beletskaya, I. P.

doi:10.1002/(sici)1521-3765(19980710)4:7<1169::aid-chem1169>3.0.co;2-h

Cited by 15 publications

(19 citation statements)

References 22 publications

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“…Experiments with polyfluorinated aryl and vinyl halides have been described previously. [21][22][23]26 [CpFe(CO) 2 ]K was obtained quantitatively (95-98%) by reductive cleavage of the dimer [CpFe(CO) 2 ] 2 with excess of NaK 2.8 alloy (0.10-0.15 ml per 1 mmol of dimer). 33 [Re(CO) 5 ]Na was prepared by the reduction of Re 2 (CO) 10 with 0.5% NaHg (30-50% excess) and purified by the low temperature crystallisation from THF.…”

Section: Methodsmentioning

confidence: 99%

“…The yields of the products discussed above are purely spectroscopic, based upon the relative integral intensity of the signals of the products and the signal of internal standard (durene or (Me 3 Si) 2 O) in 1 H NMR spectra of reaction solutions. 21 The signals were referenced to the individual products by comparison to the spectra of the isolated compounds or with the literature data for the compounds previously described, including two iron carbonyl derivatives: PhCH=CHFe(CO) …”

Section: Methodsmentioning

confidence: 99%

“…Our own studies have revealed that metal carbonyl anions are another large group of nucleophiles which can react via HME pathway with polyfluorinated aryl 21,22 and alkenyl 23 halides. Here we will give a brief account of these studies including new data on the reactions of metal carbonyl anions (carbonylates) with non-fluorinated aryl and vinyl halides.…”

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confidence: 99%

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Metal carbonyl anions as model metal-centered nucleophiles in aromatic and vinylic substitution reactions

Sazonov¹,

Ivushkin²,

Artamkina³

et al. 2003

Arkivoc

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Metal carbonyl anions as model metal-centered nucleophiles in aromatic and vinylic substitution reactions

Sazonov¹,

Ivushkin²,

Artamkina³

et al. 2003

Arkivoc

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“…By the use of anion traps (i.e, proton donors) and radical traps [25] they have been able to put forth a mechanism that challenges the traditional SET mechanism in favor of a HME mechanism (Scheme 1) [26]. The HME mechanism was shown to be the major pathway for Fp anion substitution of polyfluorinated aryl and alkenyl halides.…”

Section: Nucleophilicity Of the (η 5 -C 5 H 5 )(Co) 2 Fe Metalatementioning

confidence: 99%

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

Theys

Dudley

Hossain

2009

Coordination Chemistry Reviews

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“…We showed that nucleophilic substitution by carbonylates in perfluorinated aryl and vinyl halides can take place both as normal addition-elimination (Ad N E) (Scheme 1) and through nucleophilic attack by the carbonylate at the halogen atom (Hal = Cl, Br, I) (Scheme 2) [14][15][16][17].…”

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confidence: 99%

Halogenophilic and classical Ad N E mechanisms in nucleophilic vinylic substitution reactions involving the anions of transition metal carbonyls

2011

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The mechanism of the reaction of carbonylate anions ([M(CO) n L] -) with highly activated vinyl halides (Hal = Cl, Br, I) was investigated by the method of "anion traps" -the effect of proton donors on the composition of the reaction products. It was demonstrated that the reactions with PhCHal=C(Z) 2 (Hal = Br, I; Z = CN, CO 2 Et) and PhCN=CClI take place through initial attack by the carbonylate at the halogen atom, the reactions with PhCCl=C(CO 2 Et) 2 and PhCOCH=CHHal (Hal = Cl, I) take place through attack by the carbonylate at the ð bond (Ad N E mechanism), and in the case of E-and Z-PhCN=CHI the two mechanisms operate concurrently. The main laws determining the reaction mechanisms are analyzed.Nucleophilicity and nucleophilic substitution are among the most important concepts and processes in organic chemistry. Among the enormous variety of nucleophilic reagents a quite special class is presented by nucleophiles in which the reaction center is localized at a metal atom. The reactivity of such metal-centered anions [1-9] differs fundamentally from that observed in "classical" N-, O-, or S-nucleophiles and is largely not understood. Even in aliphatic substitution reactions metal-centered anions behave unusually, which has in due course stimulated discussion of the mechanism of single-electron transfer (SET) and its relationship with the S N 2 mechanism [10-13].For a number of years the laws governing nucleophilic vinylic and aromatic substitution involving the anions of transition metal carbonyls (carbonylates) -an extensive class of metal-centered anions widely used in synthesis and acting as intermediates in a series of practically important catalytic processes such as the carbonylation of alkyl halides and 350 0040-5760/11/4606-0350 Scheme 1. The addition-elimination mechanism (Ad N E).

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The Reaction of the [CpFe(CO)2]− Anion with Pentafluorochlorobenzene: Nucleophilic Aromatic Substitution by Halogen-Metal Exchange

Abstract: In the reaction of the [CpFe(CO) 2 ]

Cited by 15 publications

References 22 publications

Metal carbonyl anions as model metal-centered nucleophiles in aromatic and vinylic substitution reactions

Metal carbonyl anions as model metal-centered nucleophiles in aromatic and vinylic substitution reactions

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

Halogenophilic and classical Ad N E mechanisms in nucleophilic vinylic substitution reactions involving the anions of transition metal carbonyls

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