Reaction of vinyl chloride with difluorosilylene by cocondensation

Liu, Chao‐Shiuan; Hwang, Tsai-Lih

doi:10.1021/ja00505a028

Cited by 25 publications

(6 citation statements)

References 4 publications

(7 reference statements)

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“…In the interpretation of the reaction between difluorosilylene and vinyl chloride at -196 °C, the authors feel reluctant to consider the intermediate silirane. 638 The proposed mechanism Involves diradical species '(SiF2)"•. The results supporting Seyfert's postulate449 concerning involvement of monomeric SiF2 in the reaction of SiF2 with olefins have been reported.639 Section XI.A.…”

Section: Bonded Metalmentioning

confidence: 67%

Formation and properties of unstable intermediates containing multiple p.pi.-p.pi. bonded Group 4B metals

Gusel’nikov¹,

Nametkin²

1979

Chem. Rev.

299

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Section: Bonded Metalmentioning

confidence: 67%

Formation and properties of unstable intermediates containing multiple p.pi.-p.pi. bonded Group 4B metals

Gusel’nikov¹,

Nametkin²

1979

Chem. Rev.

299

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“…tains two relatively stable tertiary carbon radical tions (20), albeit with a different mode of hydride centers. The dimer from an unsymmetric alkene transfer to form the chain derivatives in the latter will yield disilacyclohexane with greater methyl two cases.…”

Section: V11 VIIImentioning

confidence: 99%

A systematic investigation of the reaction of SiF₂ with ethylene and six methyl-substituted ethylenes. I. Product yields and mechanistic conclusions

Reynolds¹,

Thompson²,

Wright³

1980

Can. J. Chem.

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SiF2 produced by the quartz tube reaction has been reacted with ethylene and six methyl-substituted ethylenes. All major products (polymers, disilacyclobutanes, disilacyclohexanes, and open chain compounds) have been characterized by a combination of 19F, 1H, 13C, and 29Si nmr spectroscopy. While polymer is always formed in highest yield, the relative proportions of other products vary significantly from alkene to alkene.Key observations concerning structures and stereochemistries and product yields are summarized. Consideration of this evidence leads to a mechanism involving attack of SiF2 on the olefin to form an excited silirane which either ring opens or relaxes to its ground state, followed in either case by further reaction.

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“…The above direct detection characterizations could not confirm the stable existence of the (SiF 2 ) x polymer, so researchers needed to prove its existence by indirect methods. First, a SiF n ( n = 1–4)-mixed air flow was prepared under high temperature, and then, unsaturated hydrocarbons (propylene, butadiene, benzene, ethylene fluoride, etc. − ), BF 3 , H 2 O, , H 2 S, GeH 4 , and PF 3 were introduced. Finally, the mixed system was rapidly frozen at low temperature, and the system was heated for the detection and characterization to confirm the presence of the polymer.…”

Section: Introductionmentioning

confidence: 99%

“…Due to the particularity of the Si–F bond, from the 1960s to the present, there have been various research reports on silicon–fluorine series, especially the various applications of SiF 2 and SiF 4 polymers. − Recently, the teams of Sen et al and Sinhababu et al also studied the separation of the stable SiF 2 monomer using a cyclic alkyl amino carbon (cAAC) ligand, but there exists no single, direct, and specific analysis of the intermediate change process. In our companion paper, we have first studied that there may be Si x F y ( x ≤ 6, y ≤ 12) series at different temperatures, mainly including Si n F 2 n +2 (2 ≤ n < 6), Si 2 F 6 , Si 3 F 8 , Si 4 F 10 , and Si 5 F 12 , and Si n F 2 n (3 ≤ n ≤ 6), Si 3 F 6 , Si 4 F 8 , Si 5 F 10 , and Si 6 F 12 .…”

Section: Introductionmentioning

confidence: 99%

Study on Pyrolytic Mechanisms of n-Perfluorosilanes Si_nF_2n+2 (2 ≤ n < 6) and Perfluorocyclosilanes Si_nF_2n (3 ≤ n ≤ 6)

et al. 2021

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In this paper, the pyrolytic mechanisms of n-perfluorosilanes Si n F 2n+2 (2 ≤ n < 6) and perfluorocyclosilanes Si n F 2n (3 ≤ n ≤ 6) are studied in terms of kinetics and thermodynamics by theoretical calculation, and the pyrolytic reaction paths of Si n F 2n+2 (2 ≤ n < 6) and Si n F 2n (3 ≤ n ≤ 6) are obtained, which can be used to guide the experimental preparation research studies and separation operations of Si n F 2n+2 (2 ≤ n < 6), Si n F 2n (3 ≤ n ≤ 6), and their intermediate substances. The results of the kinetic analysis show that the pyrolytic mechanisms of Si n F 2n+2 (2 ≤ n < 6) are as follows: first, the silicon−silicon bond breaking induces the generation of free radicals; then, in the chain transfer, the related free radicals participate in F-abstraction transfer with the molecules; and finally, the free radicals form the molecules, and the chain terminates. The F-abstraction transfer is the easiest process to initiate in the low-order silicon−fluorine substance during the chain transfer while releasing SiF 2 at the same time, whereas the generation of double free radicals is the most difficult process. The pyrolytic mechanisms of Si n F 2n (3 ≤ n ≤ 6) are as follows: first, the α−Si−Si bond breaking induces the generation of double free radicals; then, the α−Si−Si or β−Si−Si bond breaks continually in the chain transfer; and finally, the double free radicals form the molecules, and the chain terminates. SiF 2 is most easily formed by breaking during the chain transfer. In the pyrolytic processes of Si n F 2n+2 (2 ≤ n < 6) and Si n F 2n (3 ≤ n ≤ 6), the chain initiation of silicon−silicon bond breaking requires the highest bond breaking energy, which is the control step of the pyrolytic reaction. The results of the thermodynamic analysis show that the pyrolytic reactions of Si n F 2n+2 (2 ≤ n < 6) and Si n F 2n (3 ≤ n ≤ 6) are endothermic. When Si n F 2n+2 (2 ≤ n < 6) undergoes a pyrolytic reaction and the temperature is higher, the main pyrolytic products are SiF 4 and SiF 2 . When 600 K < T < 1200 K, the main pyrolytic products of Si 4 F 10 are Si 3 F 8 and SiF 2 , and when 900 K < T < 1400 K, Si 5 F 12 can also convert to Si 3 F 8 and SiF 2 . The main pyrolytic products of Si n F 2n (3 ≤ n ≤ 6) are SiF 2 . When the temperature is higher, the pyrolytic order of Si n F 2n (3 ≤ n ≤ 6) is as follows: Si 3 F 6 (ring) < Si 4 F 8 (ring) < Si 5 F 10 (ring) < Si 6 F 12 (ring). However, if the temperature is in the range of 1000 K < T < 1200 K, the pyrolytic order is the opposite.

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Reaction of vinyl chloride with difluorosilylene by cocondensation

Abstract: 49) The possibility that 1p* is not quenched by oxygen does not seem viable.Interaction of 'p* with triplet oxygen should give the triplet complex, 3(p02)\ which is the Intermediate proposed to lead to efficient quenching of 3p* by oxygen.50 (50) J. Saltlel and B.

Cited by 25 publications

References 4 publications

Formation and properties of unstable intermediates containing multiple p.pi.-p.pi. bonded Group 4B metals

Formation and properties of unstable intermediates containing multiple p.pi.-p.pi. bonded Group 4B metals

A systematic investigation of the reaction of SiF₂ with ethylene and six methyl-substituted ethylenes. I. Product yields and mechanistic conclusions

Study on Pyrolytic Mechanisms of n-Perfluorosilanes Si_nF_2n+2 (2 ≤ n < 6) and Perfluorocyclosilanes Si_nF_2n (3 ≤ n ≤ 6)

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Reaction of vinyl chloride with difluorosilylene by cocondensation

Abstract: 49) The possibility that 1p* is not quenched by oxygen does not seem viable.Interaction of 'p* with triplet oxygen should give the triplet complex, 3(p02)\ which is the Intermediate proposed to lead to efficient quenching of 3p* by oxygen.50 (50) J. Saltlel and B.

Cited by 25 publications

References 4 publications

Formation and properties of unstable intermediates containing multiple p.pi.-p.pi. bonded Group 4B metals

Formation and properties of unstable intermediates containing multiple p.pi.-p.pi. bonded Group 4B metals

A systematic investigation of the reaction of SiF2 with ethylene and six methyl-substituted ethylenes. I. Product yields and mechanistic conclusions

Study on Pyrolytic Mechanisms of n-Perfluorosilanes SinF2n+2 (2 ≤ n < 6) and Perfluorocyclosilanes SinF2n (3 ≤ n ≤ 6)

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A systematic investigation of the reaction of SiF₂ with ethylene and six methyl-substituted ethylenes. I. Product yields and mechanistic conclusions

Study on Pyrolytic Mechanisms of n-Perfluorosilanes Si_nF_2n+2 (2 ≤ n < 6) and Perfluorocyclosilanes Si_nF_2n (3 ≤ n ≤ 6)