Reactions of difluorosilylene with halogen-substituted ethylenes. A reinvestigation of the reaction mechanism

Hwang, Tsai-Lih; Pai, Yi-Ming; Liu, Chao‐Shiuan

doi:10.1021/ja00545a021

Cited by 18 publications

(3 citation statements)

References 3 publications

(3 reference statements)

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“…He found the latter to give a good approximation of the eigenfunction of Eqs ( 18) and ( 21)-( 23). We shall thus use the approximate eigenfunctions of Eqs (18) and (24). These have been listed in Ref.…”

Section: «I L)mentioning

confidence: 99%

Current driven by asymmetrical minority heating in ICRF

et al. 1983

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Current generation by asymmetric heating of a minority ion species in the ion cyclotron range of frequencies is calculated in the weak RF limit in toroidal geometry. Both trapped ions and trapped electrons produce significant modifications to the current generated. Depending on the ratio of the charge of minority to majority species, the current generated can be either sharply peaked at the centre or flattened towards the outside.

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Section: «I L)mentioning

confidence: 99%

Current driven by asymmetrical minority heating in ICRF

et al. 1983

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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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ChemInform Abstract: REACTIONS OF DIFLUOROSILYLENE WITH HALOGEN‐SUBSTITUTED ETHYLENES. A REINVESTIGATION OF THE REACTION MECHANISM

Hwang¹,

Pai²,

Liu³

1981

Chemischer Informationsdienst

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Reactions of difluorosilylene with halogen-substituted ethylenes. A reinvestigation of the reaction mechanism

Cited by 18 publications

References 3 publications

Current driven by asymmetrical minority heating in ICRF

Current driven by asymmetrical minority heating in ICRF

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

ChemInform Abstract: REACTIONS OF DIFLUOROSILYLENE WITH HALOGEN‐SUBSTITUTED ETHYLENES. A REINVESTIGATION OF THE REACTION MECHANISM

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Reactions of difluorosilylene with halogen-substituted ethylenes. A reinvestigation of the reaction mechanism

Cited by 18 publications

References 3 publications

Current driven by asymmetrical minority heating in ICRF

Current driven by asymmetrical minority heating in ICRF

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

ChemInform Abstract: REACTIONS OF DIFLUOROSILYLENE WITH HALOGEN‐SUBSTITUTED ETHYLENES. A REINVESTIGATION OF THE REACTION MECHANISM

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