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Time Resolved Gas Phase Kinetic Study of SiD + CH Najem A. Al-Rubaiey, and Robin Walsh
J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.8b01659 • Publication Date (Web): 09 May 2018 Downloaded from http://pubs.acs.org on May 9, 2018
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The Journal of Physical Chemistry
Time Resolved Gas Phase Kinetic Study of SiD2 + C2H4 Najem Al-Rubaiey1* and Robin Walsh2 1
Petroleum Technology Department, University of Technology, Baghdad, Iraq Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK *
[email protected] 2
Abstract: Time-resolved investigation of deuterium-substituted silylene (SiD2) generated by laser flash photolysis of deuterium-substituted phenylsilane (PhSiD3), was carried out to obtain rate constants for its bimolecular reaction with ethylene (C2H4). The reaction was studied in the gas phase, over the pressure range of 1-100 Torr (in SF6 bath gas) at 295K. The rate constants for SiD2+C2H4 were found to be independent of pressure, and close in magnitude to the rate constants for the reaction of SiH2+C2H4 at the high pressure limit. They are consistent with a rapid isotopic scrambling mechanism similar to that of SiH2+C2D4. Whilst silirane, the main product produced from this reaction, was too labile to be detected, vinylsilane, another possible product was ruled out by GC analysis. This reaction was shows similarities to those of SiH2 +H2 and its isotopic counterparts. Inoue and Suzuki10 (IS) reported the first time1. Introduction resolved study for the removal of SiH2 by ethene with a rate constant of 9.7±1.2 x 10-11 cm3molecule-1s-1 at 1 Torr The mechanism of the reaction of methylene with total pressure (He) by the LIF method. Subsequently Chu alkenes at gas-phase, which has been carried out over et al. 11 carried out further experiments to study the same several years and in many laboratories, is by now wellreaction using two different precursors, phenylsilane at established 1. However, progress was made complicated by 193nm and iodosilane photolysed at 248nm (LRAFKS) to check for possible artifacts. An average rate constant of the simultaneous presence of both the 3B1 (ground state) 5.35 ± 0.5 x 10-11 cm3 molecule-1s-1 was reported from both and 1A1 (excited state) of CH2 during many practical kinetics studies. Nevertheless, the mechanisms of both previous experiments. They found a moderate pressure states have now been extensively studied and clearly dependence in the range 1 to 10 Torr total pressure (using distinguished 2. He as the buffer gas). Chu et al.11 suggested that the 1 By contrast silylene exists in the A1 ground state, difference with the value of Inoue and Suzuki was most likely either due to some errors in ethene partial pressure and is uncontaminated by the presence of excited states or reactants purity. Nevertheless both measurements show when prepared by normal means 3. While early kinetics that the reaction of SiH2 with C2H4 occurs at near to studies of reactions generating silylene gave much mechanistic information by analysis of end products 4, collision rates. The pressure dependence suggested a typical third body stabilisation requirement. Our own, more recently there have been an increasing number of more extensive studies of SiH2 with ethene ,using laser direct, time-resolved studies providing an accumulating data base of absolute rate constants 5. Common reactions flash photolysis with time resolved absorption over a wider range of pressure and temperature, supported by RRKM of silylene can include insertions into Si-H, Si-OR and Omodelling 12-14, confirmed in more detail the third body H bonds or additions to C=C or C≡C π-bonds. The present study concerns the reaction of silylene stabilisation requirement of this reaction. A further study in with ethene. Silylenes are known to react with alkenes 6,7 our laboratories, of the kinetics of SiH2 with C2D4 revealed to form siliranes. The siliranes themselves are unstable that it is hardly, if at all, affected by total pressure. It is three-membered rings, difficult to detect, unless stabilised also faster than reaction of SiH2 with C2H4 at all by large groups. Thus their presence, in many cases, has experimentally achievable pressures. There is thus a only been inferred on the basis of their reactions with pressure dependent isotope effect (which diminishes as the methanol to give methoxysilanes. The addition of pressure increases). This has been explained by an isotope dimethyl- and diphenylsilylene to cis- and trans-2-butene scrambling mechanism 15, involving the intermediacy of 8 have been demonstrated to occur stereospecifically . ethylsilylene, as well as silirane. Vinylsilane was searched Rogers et al.9 studied and reported a study of the kinetics for previously 12 but not found. of reactions of silylene, produced by the pyrolysis of Silirane itself, previously undetected, has recently disilane, in the presence of alkenes. The authors suggested been made by the reaction of Si atoms with C2H6 in low a mechanism which involves the formation of siliranes as temperature matrix isolation studies 16, but not via the intermediates which can then react, either back to the reaction of SiH2 with C2H4. The addition process has been reactants or forward to the products, ethylsilylene or the subject of several theoretical studies 17-20, which vinylsilane (in the case of SiH2 + C2H4). They modelled support the idea of a virtually barrierless process. This paper reports the first study of the SiD2 + C2H4 this system over a wide range of pressures and temperatures with a complex mechanism involving a reaction at room temperature, 295K. Kinetic studies of number of estimated rate constants. SiD2 are of interest for several reasons: ACS Paragon Plus Environment
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(i) they can be compared with SiH2 data from other studies to help clarify the reaction mechanism, (ii) where SiH2 reactions show signs of pressure dependence thus making it challenging to obtain rate constants at the high pressure limit, isotopic scrambling effects give the possibility of avoiding this problem with studies using SiD2, (iii) this study will throw further light on the previous scrambling mechanism 15 proposed for SiH2+C2D4. 2. Spectrum of SiD2 The preparation procedure of SiD2 precursor (PhSiD3) and the identification of the absorption spectrum of SiD2 have been explained in detail elsewhere 21,22. Briefly, Mason et al. 22 were the first to study the kinetics of SiD2 in the gas phase. This was carried out using the laser flash photolysis kinetic absorption technique. They recorded a portion of the highly resolved vibronic absorption spectrum of in the range 17384-17391 cm-1 and employed the strongest rotational line at 17387.07cm-1 to record the measurements.. This peak was consequently selected to monitor SiD2 in this work. It was predicted that this peak intensity is roughly 1/4 of that for the transition employed to observe SiH2 in investigations under identical conditions 22. 3. Experimental Setup The apparatus, equipment and chemicals for these studies have been described in detail elsewhere 21. Briefly, a home-made vacuum line was linked to photolysis cell fixed with crown glass end windows (at Brewster’s angle). This vacuum line was pumped by a commercial rotary pump. The deuterated-silylene species (SiD2) was produced by flash photolysis at 193 nm of deuteratedphenylsilane, PhSiD3, using an excimer laser (Oxford KX2) The laser pulses produced have energies in the range of 50-200mJ per pulse (pulse width, 10 ns and repetition rate of 1 Hz). The concentration of SiD2 was observed by means of a Coherent 699–21 single-mode dye laser pumped by an Innova 90–5 Ar+ laser. This laser supplies tunable emission in the wavelength range of 560-610 nm. The recording laser beam was multi-passed inside the reaction cell (by use of White’s optics) between 24-48 times, to obtain a path length of 1.0 - 2.0m. In this particular study, the recording laser was adjusted to 17387.07 cm-1. A differential amplifier was used and linked to two photodiodes (one from the reaction cell and the other the reference). They then fed into transient recorder (Datalab Dl910/ 20 MHz resolution). An external probe connected to the transient recorder was triggered by the excimer laser via the radiofrequency noise, and interfaced to a microcomputer (using a Camplus commercial interface). The traces produced throughout the experiments were then stored on the microcomputer which was used to display and analyze the signals.
Gas mixtures for photolysis were made up, containing 3 mTorr of PhSiD3, and between 0 to 20 mTorr of C2D4, together with inert diluent (SF6) up to total pressures of 100 Torr. Pressures were measured by capacitance manometers (MKS Baratron). All gases used in this work were deaerated prior to use. An attempt was made to identify vinylsilane as a product of the room temperature reaction of SiH2 with C2H4. In previous investigations 23 at high temperature this had been identified as a product. The end product analysis experiments were performed using a static photolysis cell similar to those described in this work. Photolysis experiments were carried out using an excimer laser at 193 nm. A Perkin-Elmer Model 8310 gas chromatograph with a flame ionisation detector and porapak Q, 4m and porapak T, 2m columns were used. There was no peak identified with retention time appropriate for a C2Si containing compound. vinylsilane particularly could be ruled out from the information of the authentic sample retention time. On the other hand, silirane itself would certainly be formed, but was most likely too sensitive to survive passing through the chromatograph column. 4. Results and Discussion The reaction of SiD2 with C2H4 was examined at room temperature (295K). Signal decay constants, which were exponential, were obtained by averaging 10 photolysis laser shots and were found to provide excellent first-order kinetics fits. The linear dependence of the pseudo first order decay constants on C2H4 partial pressures, within reasonable scatter, shown in figure 1, confirms the second order kinetics of this reaction. Similar plots were obtained at other total pressures. The second order rate constant data, obtained from the slopes of these plots, are shown in table 1.
Figure 1. Second-order plot for SiD2 + C2H4 reaction at T= 295K, and PT= 10 Torr in SF6. Uncertainties are indicated by error bars.
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Table 1 Second order rate data for the reaction of SiD2 + C2H4 at T= 295K. PT/Torr 1 3 10 30 100
k/10-11 cm3 molecule-1 s-1 12.8 ± 2.0 26.5 ± 3.2 22.9 ± 1.7 25.4 ± 2.6 20.7 ± 1.3
As can be seen, the second order rate constants between 3 and 100 Torr are constant within the experimental scatter. The weighted average of their values gives k = 22.85±1.7 10-11 cm3 molecule-1 s-1. The value at 1 Torr total pressure is approximately a factor of two lower. While this may suggest a slight pressure dependence, it seems probable that it has been exaggerated by experimental error. As argued previously for the reaction of SiH2 + C2D410, this constancy of the observed bimolecular rate constant for SiD2 removal by C2H4 suggests that it approximates the high pressure-limiting rate constant for SiH2 addition to C2H4 12,13 (but see below). The absolute rate constants obtained here are compared with those of other studies in table 2. Table 2. Absolute rate comparison for the reactions of silylene with some substrates at 298K and at their high pressure limitsa. Silyene SiH2 SiD2
k/10-11 cm3molecule-1s-1 C2H4 C2D4 H2 D2 35 ± 35 ± 0.24 ± 0.26 ± 12b 12b 0.05c,d 0.07e 22.9 ± 0.38 ± 0.17 ± 1.7 0.02f 0.04c,d
dependence. This might partly account for the apparent difference between the rate constant values found here and previously12-15. A further attempt was made to search for vinylsilane as a product of the room temperature reaction of SiH2 with C2H4. An earlier attempt 12 had been unsuccessful, but in previous investigations23 at high temperature this had been identified as a product. There was no peak identified with retention time appropriate for a C2Si containing compound. Vinylsilane in particularly could be ruled out because no GC peak was found with an authentic sample retention time. Silirane itself was almost certainly formed, but it would have been too sensitive to survive passage through the chromatograph columns 26. 5. Mechanism of the Reaction The much lesser pressure dependence of the reaction of SiD2, compared with SiH2, with C2H4 strongly suggests that the addition reaction channel is affected by another process. In the previous work of SiH2 + C2D4 we pointed out that the substantial isotope effect, which is pressure dependent, is not consistent with a simple process, but rather points to an isotopic scrambling mechanism15 in which re-elimination of SiH2 from the vibrationally unquenched silirane-(d4) is supplemented by parallel pathways giving SiHD and SiD2. The analogous process for the present reaction is shown in Figure 2. Here reelimination of SiD2 from the vibrationally unquenched silirane-(d2) is supplemented by parallel pathways giving SiHD and SiH2.
a
See text Obtained by extrapolation using RRKM theory12-15. c Obtained by extrapolation using an empirical procedure21. d Ref. 24. e PT= 1 Torr in He (pressure independent reaction)25. f PT= 5 Torr in SF6 22. b
Some important inferences can be made from the numbers in table 2. For all reactions shown, the rate constants of SiD2 and SiH2 with the same substrate are fairly close to one another at the high pressure limit. In particular the rate constants for SiD2+C2H4 are within experimental error of those for SiH2+C2D4. Nevertheless that for SiD2+C2H4 is still some 35% lower than that for SiH2+C2D4. However, RRKM modelling revealed that in the reaction of SiH2 with C2D4 there was a very small pressure dependence15. We have not carried out RRKM modelling for the present reaction and it remains possible that there could be a slight undetected pressure
Figure 2. The scrambling mechanism suggested for the reaction of SiD2+C2H4. In figure 2, the addition reaction of SiD2 to the πsystem of C2H4 produces vibrationally excited silirane-(d2) in which only a small fraction (one channel) re-dissociates
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back to reactants (SiD2 + C2H4). This is because the deuterium exchanges with the hydrogen via the formation of ethylsilylene-(d2). To fit with our results such a process must occur over a very short timescale and be reversible. This effectively means that hydrogen atom movement (H or D) is possible around the silirane ring, thus scrambling the label before decomposition back to a silylene and ethene. Silylenes such as ethylsilylene are much more stable than carbenes relative to their sila-alkene or alkene isomers and therefore become more readily accessible to thermal processes. This is supported by Potential Energy Surface calculations 15. At pressures below the high pressure limit, the various silirane(d2) intermediates may decompose to form SiHD + C2H3D or SiH2 + C2H2D2 as well as SiD2 + C2H4. These other possibilities make the chance of getting SiD2 back from silirane small, ca. 6.7% on statistical grounds. However this process may not be complete and the interesting question is how fast the silirane decomposes to the reactants compared to the scrambling. The rate constants measured at the higher pressure limit for SiH2 + C2D4 10 correspond to the high pressure limit of the more pressure dependent rate constants for SiH2 + C2H4 12,13 , showing good consistency between the two systems. They show agreement at high pressure but not at lower pressures. The rate constants measured here for SiD2 + C2H4 are approximately pressure independent and within error limits, the same as those for SiH2 + C2D4. However it is possible that, because of isotopic differences affecting the individual steps of the mechanism of figure 2, the extent of scrambling is less for the present system than for SiH2 + C2D4. The investigation of this (requiring calculation of vibration frequencies of the various silirane-d2 intermediates, as well as RRKM calculations) is beyond the scope of this study. The non-finding of vinylsilane confirms the result of our earlier study 13. The reason for its finding as a product at high temperatures 9, but absence as a product at room temperature, is discussed in our earlier study 13. The data for the SiH2/SiD2 + H2/D2 systems in table 2 were included because they show similar characteristics to those for SiH2/SiD2 + C2H4/C2D4. The isotopically pure systems, SiH2 + H2 and SiD2 + D2 show pressure dependent rate constants, which have to be extrapolated to obtain the high pressure limiting values. The isotopic cross over systems, SiH2 + D2 and SiD2 + H2 have rate constants which are much higher and plausibly close to the high pressure limits. An isotopic scrambling process for SiH2 + D2, via SiH2D2, has already been proposed 25. The rate constants for SiH2 + D2, have been found to be almost constant between 3 and 100 Torr (in SF6) 24. Possible further work includes a more extended kinetic investigation of SiD2 + C2H4 over a wider range of pressure and temperature and RKKM calculations on this reaction.
6. Conclusion SiD2, generated via the laser flash photolysis of PhSiD3 has been detected via a rotational transition in its A(1B1) X(1A1) absorption band. A single rotational line at 17387.07 cm-1 was used in this work to monitor SiD2 removal. Rate constants were obtained at room temperature for the reaction of SiD2 with C2H4 in the pressure range 1-100 Torr (in SF6). The rate constant was found to be invariant within the scatter, and plausibly represents the high pressure limit. This is consistent with results obtained from earlier kinetics studies of SiH2+C2H4 and SiH2 + C2D4. Acknowledgment he authors would like to express their sincere appreciation to the Department of Chemistry, University of Reading, UK which provided the possibility to complete this work, and to the Iraqi Ministry of Higher Education for the award of a research scholarship (to N. A-R.) .A special thanks is also due to Dr. Ben Paul Mason for his help with the spectrum of SiD2. References 1. 2.
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