A new mechanism of nucleophilic vinylic substitution and unexpected products in the reaction of chlorotrifluoroethylene with [Re(CO)5]Na and [CpFe(CO)2]K

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

doi:10.1016/j.jorganchem.2005.12.050

Cited by 7 publications

(9 citation statements)

References 37 publications

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“…A very facile 1,2‐shift of transition metal carbonyl groups in carbenoid salts, such as Na[(CO) 5 ReCF 2 CFCl], was studied previously and supported both by experimental and computationall data . Its NBO analysis shows the same bonding pattern (Figure ) – nucleophilic migration of (CO) 5 Re‐group to the carbenoid empty orbital.…”

Section: Resultssupporting

confidence: 59%

“…Such carbenes rearrange spontaneously to the corresponding alkenes during geometry optimization, which precludes the location of the transition state. We previously observed such behaviour in carbenes bearing β ‐metal carbonyl groups, now it turns out that barrierless 1,2‐migration is common for other heavy element R n E fragments. The attempts to find the transition state for 1,2‐migration were continued on the model of β ‐trimethylsilyl carbene using various DFT functionals and ab initio methods (MP2, MP4, QCISD, CCSD(T)).…”

Section: Resultsmentioning

confidence: 81%

“…Inclusion of solvation effects or of larger [NMe 4 ] cation increases the reaction barrier by several kcal/mol, but does not alter the above conclusion. In case of the 5 th ‐period elements – R 3 Sn, R 2 Sb and RTe groups, the barriers become as low as 5–7 kcal/mol, meaning that the 1,2‐migration process should be as easy as for transition metal carbonyl fragments, for which there is experimental evidence supporting this mechanism …”

Section: Resultsmentioning

confidence: 99%

“…The same mechanism with 1,2‐shift of the nucleophile was shown to be responsible for the substitution of chloride in chlorotrifluoroethylene with [Re(CO) 5 ] – and [CpFe(CO) 2 ] – metal carbonyl anions . Metal carbonyl groups turn out to migrate even more easily than arylthio groups, since thiolate nucleophiles react with chlorotrifluoroethylene by an ordinary addition‐elimination mechanism, substituting fluoride from CF 2 ‐group (Scheme ).…”

Section: Introductionmentioning

confidence: 83%

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1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

et al. 2016

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The 1,2‐shift of β‐substituent to the carbenic or carbenoid centre is one of the primary reaction pathways for these intermediates. In the present work the 1,2‐shift of various element‐centered groups in carbenoid anions [RnECF2CFCl]– (E=C, N, Si, Ge, Sn, P, As, Sb, S, Se, Te, R=Me) is for the first time examined with the help of density functional theory calculations. The calculations were performed on the models of free carbenoid anions [RnECF2CFCl]– and their Na+ and [NMe4]+ salts. In all cases the 1,2‐shift of the RnE‐groups formed by the elements of the third and subsequent periods was calculated to be much more facile than for carbon‐centred groups. Calculated ΔG≠ are as low as 4–6 kcal/mol for the 5−th period Me3Sn‐ and Me2Sb groups. An even more facile 1,2‐shift precludes the existence of the corresponding β‐element substituted carbenes. Periodicity trends, correlation analysis and NBO analysis of the transition state structures were used to discriminate between different intrinsic mechanisms. In free carbenoid anions the main mechanisms of 1,2‐shift of RnE‐groups are: a) electrophilic shift of R3E‐ (E= Si, Ge, Sn) and Ph‐groups; b) nucleophilic shift of RS‐ group c) dyotropic‐type pathway for RS‐, RSe‐, RO‐, R2N and R3C‐ groups. In carbenoid ion pairs: a) nucleophilic shift of RnE‐ (E=Si, Ge, Sn P, As, Sb) and Re(CO)5‐ groups; b) nucleophilic substitution involving the lone pair of RS‐, RSe‐ and R2N‐ groups.

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Section: Resultssupporting

confidence: 59%

Section: Resultsmentioning

confidence: 81%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 83%

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1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

et al. 2016

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“…Palladium compounds are widely utilized for these reactions with ethylene, norbornenes, the other alkenyl compounds, alkenyl halides, aryl alkenyl and alkenyl esters 164–179. The other metal compounds are iron,180–182 manganese183, 184 and rhodium metal compounds 185…”

Section: Synthesis Of Carbonyl Group‐containing Organometallic Intrammentioning

confidence: 99%

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

Omae¹

2010

Applied Organom Chemis

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Carbonyl group-containing organometallic intramolecular-coordination five-membered ring compounds are easily synthesized by the following five reaction methods: (1) cyclometalation, especially, orthometalation reactions; (2) the reactions of the moieties of an unsaturated carbon-carbon bond attached to a carbonyl group (C C-CO, C C-CO); (3) the reactions of an unsaturated carbon-carbon bond with carbon monoxide (C C and CO, C C and CO); (4) carbonylative ring expansion reactions; and (5) others. These compounds are very easily and regio-specifically synthesized with many kinds of metal compounds, including both transition metals and main group metals. Many of such the reactions are easily applied to organic syntheses.

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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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A new mechanism of nucleophilic vinylic substitution and unexpected products in the reaction of chlorotrifluoroethylene with [Re(CO)5]Na and [CpFe(CO)2]K

Cited by 7 publications

References 37 publications

1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

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

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A new mechanism of nucleophilic vinylic substitution and unexpected products in the reaction of chlorotrifluoroethylene with [Re(CO)5]Na and [CpFe(CO)2]K

Cited by 7 publications

References 37 publications

1,2-Shift of Element-Centered Groups (RnE) in Carbenoid Anions [RnECF2CFCl]−and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

1,2-Shift of Element-Centered Groups (RnE) in Carbenoid Anions [RnECF2CFCl]−and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

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

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1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study