Kinetics of the thermal decomposition of methyldisilane and trisilane

Vanderwielen, A. J.; Ring, M. A.; O’Neal, H. E.

doi:10.1021/ja00838a008

Cited by 67 publications

(42 citation statements)

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“…Since propane was not a reaction product, alkane elimination [comparable to reaction (3)] does not occur to any observable degree. the two hydrogen eliminations [reactions (14) and (15) Direct elimination of propylene as a primary process can also be excluded. Such a reaction would generate rather large yields of silane,* but in actual fact silane yields were small.…”

Section: Primary Process Reactionsmentioning

confidence: 99%

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Kinetics and mechanism of the shock induced thermal decomposition of n‐propylsilane

Sawrey

O’Neal

Ring

et al. 1984

Int J of Chemical Kinetics

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Section: Primary Process Reactionsmentioning

confidence: 99%

“…(d) Reactions (12), (13), (14), R = R' = H; reactions (15), (16) (12), (13), (14) parameters listed. Reaction (15) log A = 11.2, E = 0; reaction (16) log A = 16.0, E = 59,000; reaction (17) log A = 14.3, E = 54,000; reaction (18) log A = 11.0, E = 0; reaction (19) log A = 16.2, E = 60,000; reaction (20) log A = 14.5, E = 55,000.…”

Section: Calcmentioning

confidence: 99%

Kinetics and mechanism of the shock induced thermal decomposition of n‐propylsilane

Sawrey

O’Neal

Ring

et al. 1984

Int J of Chemical Kinetics

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“…The chromatographic behavior of this product suggests that it contains four carbon atoms. It has been compared chromatographically with the accessible SiC4H, ( n = 6, 8, 10,12) compounds, and it is not identical with any of them as indicated by the retention times given in Table I. 3. An empirical formula 31SiC4H6 is indicated by its formation in nearly identical 20 f 3% yields from 1:l phos- a Flow rate data: SF-96 60 mL/min (25 "C).…”

Section: Resultsmentioning

confidence: 99%

Reactions of recoiling silicon atoms with phosphine-diene mixtures and the question of silylene intermediates

Hwang¹,

Gaspar²

1978

J. Am. Chem. Soc.

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Reactions of silicon atoms recoiling from the 3'P(n,p)31Si nuclear transformation in phosphine-butadiene mixtures yield [31Si]-1 -silacyclopent-3-ene, also obtained in 46% yield from reaction of thermally generated SiH2 with butadiene, and a product believed to be [31Si]-l-silacyclopenta-2,4-diene. The variation of product yields with the composition of PH3-SiH4-C4H6 recoil reaction mixtures casts doubt on the participation of ground-state singlet silylene 31SiH2 as a reactive intermediate, as does the failure to detect any of the thermal adduct of silylene to cyclopentadiene l-silacyclohexa-2,4-diene from the reactions of 31Si in P H~-S~H~-C -C~H~ mixtures. Alternative mechanisms are considered. Thermally generated Me2Si does not abstract hydrogen atoms from Me,SiH, but inserts into the Si-H bond.

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“…[22,23] Katzer, Sax et al [24][25][26] have performed extensive theoretical investigations on the thermochemistry of silicon hydrides and the effects of anharmonic vibrations on thermochemistry. Interest in the substituted silylene addition and elimination reactions of silicon hydrides extends beyond Si-H systems to hybrid silicones, [27] chlorosilicon hydrides, [28][29][30][31] Si-C hydrides, [32][33][34][35][36] and Si-Ge heterostructures. [37][38][39] Nonetheless, detailed exploration of substituted silylene addition has not been extended beyond silylsilylene, and it is precisely this information that is necessary to describe cluster growth kinetics.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of Substituted Silylene Addition and Elimination in Silicon Nanocluster Growth Captured by Group Additivity

et al. 2010

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Accurate rate coefficients for 40 bimolecular substituted silylene addition reactions for silicon hydrides containing up to nine silicon atoms are calculated using the G3//B3LYP method. The overall reactions exhibit two steps: the reactants first meet to form an adduct, which then converts into a saturated silicon hydride. Values for the single-event Arrhenius pre-exponential factor, A, and the activation energy, E(a), are calculated from the G3//B3LYP rate coefficients corrected for internal rotations, and a group additivity scheme is developed to predict A and E(a). The values predicted by group additivity are more accurate than structure-reactivity relationships currently used in the literature, which rely on representative A values and the Evans-Polanyi correlation. The structural factors that have the most pronounced effect on A and E(a) are considered, and the presence of rings is shown to influence these values strongly.

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Kinetics of the thermal decomposition of methyldisilane and trisilane

Cited by 67 publications

References 1 publication

Kinetics and mechanism of the shock induced thermal decomposition of n‐propylsilane

Kinetics and mechanism of the shock induced thermal decomposition of n‐propylsilane

Reactions of recoiling silicon atoms with phosphine-diene mixtures and the question of silylene intermediates

Kinetics of Substituted Silylene Addition and Elimination in Silicon Nanocluster Growth Captured by Group Additivity

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