Nucleophilic vinylic substitution with transition metal carbonyl anions—a rare case of a halophilic reaction mechanism

Sazonov, P. K.; Artamkina, G. A.; Khrustalev, Victor N.; Antipin, M. Yu.; Beletskaya, I. P.

doi:10.1016/s0022-328x(03)00531-x

Cited by 16 publications

(24 citation statements)

References 39 publications

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“…Halo(acyl)rhenates contain structurally intact fragments of aryl (alkenyl) carbanion and Re(CO) 5 Hal, and their formation by a carbanion addition reaction, having good literature precedence, 29 may be considered as an "autotrapping" of the HME intermediates. 23 As it is already evident only the heavy halogen (Cl, Br, I), but not fluorine is substituted by carbonylates. This is noteworthy, since common "electronegative" nucleophiles, 30 and even "soft" carbanions 22,23 , substitute fluorine in such substrates as 1-Br, 1-Cl or 2, as is only to be expected for Ad N E mechanism (shown on Scheme 3 for an alkenyl halide).…”

Section: Resultsmentioning

confidence: 95%

“…23 As it is already evident only the heavy halogen (Cl, Br, I), but not fluorine is substituted by carbonylates. This is noteworthy, since common "electronegative" nucleophiles, 30 and even "soft" carbanions 22,23 , substitute fluorine in such substrates as 1-Br, 1-Cl or 2, as is only to be expected for Ad N E mechanism (shown on Scheme 3 for an alkenyl halide).…”

Section: Resultsmentioning

confidence: 95%

“…bromotrifluoroethylene (2), 1,2-difluoro-2-t-Bu F -1-bromo and 1-chloro ethylenes (3-Br and 3-Cl) 23 and 2-t-Bu F -substituted 1-chlorohexafluorocyclopentene (4) 26 (Fig 1). Yet, in several other polyfluoroalkenyl chlorides, namely Z-and E-chlorodifluorostyrenes 26,27 and 1-chloro-2-(trifluoromethyl)hexafluorocyclopentene 26 ( Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Halophilic reactions with polyfluoroalkenyl halides 3-Br and 3-Cl proceed with retention of their original Z configuration in all the reaction products: σ-alkenyl metal complexes, halo(acyl)rhenates and protodehalogenated alkenes R F H. 23 On the whole the observed chemistry is not consistent with SET mechanism and free radical intermediates (Scheme 1), nor with the classical Ad N E mechanism (Scheme 3), but agrees well with HME mechanism and aryl (alkenyl) carbanion intermediates. Arguments against SET for the reactions with alkenyl halides have been already discussed in full detail elsewhere.…”

Section: Resultsmentioning

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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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: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

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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Carbonylmetallates—A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions

Sazonov

Beletskaya

2016

Chemistry A European J

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Carbonylmetallates, [M(CO)(n)L](-), anionic transition-metal carbonyl complexes, represent a large family of metal-centered nucleophiles, and studying carbonylmetallates allows us to understand the differences in the behavior of the metal-centered complexes versus heteroatom-based nucleophiles. The mechanisms of carbonylmetallate reactions with aryl- and alkenyl halides have been examined by employing radical and, especially, carbanion trapping techniques. Carbonylmetallates show a marked preference for halogenophilic attack, and nucleophilic substitution with carbonylmetallates is often not a direct process, but proceeds through the initial attack at halogen with subsequent coupling of carbanion and HalM(CO)(n)L intermediates. Factors governing the competition between the halogenophilic and more common "carbophilic" reaction pathways, as well as the means of predicting the actual course of reaction are discussed. The review also considers other aspects of carbonylmetallate reactivity, including ion-pairing effects, radical-mediated nucleophilic substitution pathways, and the carbonylmetallate nucleophilicity scale in the reactions with π-electrophiles.

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Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)₂Os₃(CO)₁₀]

et al. 2017

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A reaction has been found and investigated that demonstrates the potential for coordination, activation, and transformation of three organic molecules, namely, two dichloromethane molecules and one amine molecule, in the coordination sphere of the [(µ‐H)Os3(CO)10]– carbonylate anion, which is formed in situ from the deprotonation of [(µ‐H)2Os3(CO)10]. This reaction is very intricate and comprises such steps as the nucleophilic substitution of chloride ions by cluster carbonylate anions in the halocarbons, C–H, C–N, and C–Cl bond cleavage, and C–C and C–N bond formation under unusually mild conditions for such reactions leading to the formation of the CH=CH2‐ or CH=CHNR2‐bearing complexes [(µ‐Cl)Os3(µ2‐σ,π‐CH=CH2)(CO)10] and [(µ‐H)Os3(µ‐CH=CHNR2)(CO)10]. The reaction is sensitive to the nature of the halogen in the halocarbon. When bromine or iodine was used in place of chlorine in the halohydrocarbons, [(µ‐H)Os3(µ‐X)(CO)10] (X = Br, I) clusters were obtained in good yields, which apparently indicates the replacement of the SN2 mechanism by SN2Hal.

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Nucleophilic vinylic substitution with transition metal carbonyl anions—a rare case of a halophilic reaction mechanism

Cited by 16 publications

References 39 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

Carbonylmetallates—A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions

Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)₂Os₃(CO)₁₀]

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Nucleophilic vinylic substitution with transition metal carbonyl anions—a rare case of a halophilic reaction mechanism

Cited by 16 publications

References 39 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

Carbonylmetallates—A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions

Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)2Os3(CO)10]

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Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)₂Os₃(CO)₁₀]