<b>Silicon-Silicon Bond Dissociation Energies in Disilane and Hexachlorodisilane</b>

Steele, W. C.; Stone, F. Gordon A.

doi:10.1021/ja00877a049

Cited by 27 publications

(8 citation statements)

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“…Any proposed mechanism (A or B) must explain the various disilanes formed, the change in the relative ratios of these disilanes formed in the static pyrolyses compared to the flow pyrolyses (see Table I), and the fact that the ratio, R, of the quantity of mixed silanes (SiH4_zDz, where x = 1-3) vs. the quantity of disilanes produced varied from about 30/1 in the static pyrolyses to about 2.5/1 in the flow pyrolyses. We feel that all of these results can be explained wholly on the basis of mechanism B with two additional processes: (1) hydrogen abstraction from silane by silyl radicals SiHa F SiD4 -= S1H3D F S1D3 (14) and most important (2) the decomposition equilibrium of disilanes into silene and silane Si2H6 SiH4 F SiH2 (15) Reaction 14 provides a path for mixed silane production, while reaction 15 is a process by which both mixed silanes and disilanes can be formed. Reaction 14 should be operative in both the flow and static pyrolyses, while reaction 15 should be very important in the static pyrolysis but relatively unimportant in the flow pyrolysis.…”

Section: Discussionmentioning

confidence: 93%

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Pyrolysis of monosilane

Ring¹,

Puentes²,

O’Neal³

1970

J. Am. Chem. Soc.

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Section: Discussionmentioning

confidence: 93%

“…Inclusion into the overall mechanism suggests that disilane decomposition into silene and silane is fast relative to the overall silane decomposition. The reverse of reaction 15 must also be extremely fast (see ref 12).…”

Section: Discussionmentioning

confidence: 99%

Pyrolysis of monosilane

Ring¹,

Puentes²,

O’Neal³

1970

J. Am. Chem. Soc.

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“…General operation of the instrument was checked by examining the energy dependence of the cross section for the formation of ArD+ in Ar+-D2 collisions over the range [1][2][3][4][5][6][7][8][9][10] eV (laboratory energy). The dependence of the cross section on the kinetic energy of Ar+ was found to be in satisfactory agreement with that found by Teloy and Gerlich13 over the given energy range.…”

Section: Methodsmentioning

confidence: 99%

Ion-molecule reactions in silane-tetrafluoromethane mixtures

Krause¹,

Lampe²

1977

J. Phys. Chem.

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The reactions of Si+, SiH+, SiH2+, and SiH3+ with CF4 and the reactions of F+, CF+, CF2+, and CF3+ with SiH4 have been investigated by tandem mass spectrometry. In related experiments the reactions of SiH3+ with CF3H have been studied also. Reaction cross sections have been determined over the range of 1-4 eV in the laboratory system and phenomenological rate constants for a reactant-ion energy of 1 eV are reported. The major reaction of positive ions containing fluorine with SiH4 is H~abstraction and the major reaction of positive silicon ions with CF4 is F~abstraction. Also observed in the reactive encounters of CF3+ and CF2+ with SiH4 are products in which extensive redistribution of F and H between carbon and silicon centers has occurred. These redistribution reactions, which involve the breaking and reforming of up to six bonds, must occur within a single collision complex. A mechanism for this redistribution, in the case of the reaction of CF3+ with SiH4, is proposed in which the collision complex is held together by alternating hydrogen and fluorine bridges.

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“…diameter) leading directly into the ionization region of a Bendix Model 14-101 time-of-flight mass spectrometer. Total pressures employed in the photolysis ranged from 5 to 20 Torr, with NO concentrations usually in the range of 1-9 mol % although in a few experiments NO concentrations as high as 50% were used.…”

Section: Methodsmentioning

confidence: 99%

Mass spectrometric study of the mercury-photosensitized reactions of silane and methylsilane with nitric oxide

Kamaratos¹,

Lampe²

1970

J. Phys. Chem.

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Silyl radicals and methylsilyl radicals formed by Hg (63Pi)-photosensitized decomposition of silane and methylsilane, respectively, react efficiently with nitric oxide to produce siloxanes and nitrous oxide as the principal products. The reaction is a chain reaction at room temperature which, from the evidence at hand, is proposed to involve SiH80(SiH20)" and CH3SiH20(CH3SiH0)" radicals, in = 0,1, 2, .. .), as well as the primary radicals SiH8 and CH3SiH2.It has previously been reported from this laboratory that, when nitric oxide at low concentration is employed at room temperature as a scavenger of methyl radicals, trimethylhydroxylamine is the stable product of the radical-scavenging process and is formed by the successive addition of methyl radicals to nitric oxide.2•8 Recent studies of the mercury-photosensitized decomposition of monosilane4•5 have suggested that the formation of the predominant silicon-containing product, disilane, may occur via the combination of silyl radicals, viz. SiH3 + SiH3 -> Si2He(1) and, in this respect, at least, may resemble mechanistically the analogous ethane formation in systems containing methyl radicals. However, despite this sim-

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Silicon-Silicon Bond Dissociation Energies in Disilane and Hexachlorodisilane

Cited by 27 publications

References 0 publications

Pyrolysis of monosilane

Pyrolysis of monosilane

Ion-molecule reactions in silane-tetrafluoromethane mixtures

Mass spectrometric study of the mercury-photosensitized reactions of silane and methylsilane with nitric oxide

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