Amine-Promoted Disproportionation and Redistribution of Trichlorosilane:  Formation of Tetradecachlorocyclohexasilane Dianion<sup>1</sup>

Choi, Seok-Bong; Kim, Beon-Kyu; Boudjouk, Philip; Grier, Dean G.

doi:10.1021/ja002831a

Cited by 89 publications

(80 citation statements)

References 10 publications

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“…A number of new "inverse sandwich" compounds were isolated (e.g., [ n Bu 4 , where the Si 6 ring becomes planar upon coordination of the perhalocyclohexasilane, thus illus-trating the predictive power of our strategy toward suppressing the PJT effect. The comprehensive computational analysis of Si 6 Cl 12 electronic structure allowed us to identify the main cause of the PJT effect suppression originating from filling in the initially empty UMOs of Si 6 Cl 12 with electrons of the adduct (e.g., Cl -).…”

Section: Discussionmentioning

confidence: 99%

Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn–Teller effect

Pokhodnya

Olson²,

Dai³

et al. 2011

The Journal of Chemical Physics

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We report the experimental and theoretical characterization of neutral Si(6)X(12) (X = Cl, Br) molecules that contain D(3d) distorted six-member silicon rings due to a pseudo-Jahn-Teller (PJT) effect. Calculations show that filling the intervenient molecular orbitals with electron pairs of adduct suppresses the PJT effect in Si(6)X(12), with the Si(6) ring becoming planar (D(6h)) upon complex formation. The stabilizing role of electrostatic and covalent interactions between positively charged silicon atoms and chlorine atoms of the subject [Si(6)Cl(14)](2-) dianionic complexes is discussed. The reaction of Si(6)Cl(12) with a Lewis base (e.g., Cl(-)) to give planar [Si(6)Cl(14)](2-) dianionic complexes presents an experimental proof that suppression of the PJT effect is an effective strategy in restoring high Si(6) ring symmetry. Additionally, the proposed pathway for the PJT suppression has been proved by the synthesis and characterization of novel compounds containing planar Si(6) ring, namely, [(n)Bu(4)N](2)[Si(6)Cl(12)I(2)], [(n)Bu(4)N](2)[Si(6)Br(14)], and [(n)Bu(4)N](2)[Si(6)Br(12)I(2)]. This work represents the first demonstration that PJT effect suppression is useful in the rational design of materials with novel properties.

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Section: Discussionmentioning

confidence: 99%

Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn–Teller effect

Pokhodnya

Olson²,

Dai³

et al. 2011

The Journal of Chemical Physics

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“…13 We recently developed a unique synthetic route to a novel liquid silicon precursor, cyclohexasilane ͑Si 6 H 12 ͒. 14,15 Readily purified by distillation, Si 6 H 12 is a promising alternative to silane ͑SiH 4 ͒ in chemical vapor deposition ͑CVD͒ and may be enabling for directwrite fabrication of printed electronics. Si 6 H 12 contains only silicon and hydrogen and can be transformed into solid polydihydrosilane ͓-͑SiH 2 ͒ n -͔ by light activation or thermal treatment whereby radical polymerization occurs upon scission of Si-Si bonds.…”

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confidence: 99%

Si[sub 6]H[sub 12]/Polymer Inks for Electrospinning a-Si Nanowire Lithium Ion Battery Anodes

Schulz

Hoey

Smith

et al. 2010

Electrochem. Solid-State Lett.

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Amorphous silicon nanowires ͑a-SiNWs͒ have been prepared by electrospinning a liquid silane-based precursor. Cyclohexasilane ͑Si 6 H 12 ͒ was admixed with poly͑methyl methacrylate͒ ͑PMMA͒ in toluene giving an ink that was electrospun into the Si 6 H 12 /PPMA wires with diameters of 50-2000 nm. Raman spectroscopy revealed that thermal treatment at 350°C transforms this deposit into a-SiNWs. These materials were coated with a thin carbon layer and then tested as half-cells where a reasonable plateau in electrochemical cycling was observed after an initial capacity fade. Additionally, porous a-SiNWs were realized when the thermally decomposable binder polypropylene carbonate/polycyclohexene carbonate was used as the polymer carrier.There is a marked international interest in replacing carbonbased materials with silicon or silicon-based compounds as anodes in next-generation lithium ion batteries ͑LIBs͒. When compared to graphite-based Li 1 C 6 with a specific capacity of 372 mAh/g, the lithium-silicon phase ͑Li 22 Si 5 ͒ exhibits a theoretical specific capacity of ϳ4200 mAh/g. 1 While this represents a storage capacity improvement of more than 1 order of magnitude, fully lithiated Li 22 Si 5 undergoes a Ͼ300% volume expansion often resulting in mechanical failure leading to subsequent loss of capacity within a few cycles.Many approaches have been employed toward the development of silicon-containing anodes. Wang and Kumta utilized a homogeneous dispersion of silicon particles within a suitable matrix to give composites that improve mechanical stability and electrical conductivity vs pure silicon. 2 Chan and co-workers grew SiNWs via a vapor-liquid-solid ͑VLS͒ route by reacting SiH 4 gas with Au. 3 More recent articles highlight the ability to form core-shell SiNWs where an inner crystalline wire that evolved from the melt-growth surface is surrounded by an amorphous silicon ͑a-Si:H͒ phase. 4 A new vapor-induced solid-liquid-solid ͑VI-SLS͒ route to SiNWs uses bulk silicon powders thus offering the possibility of scalable and cost-effective mass manufacture without the need for a localized catalyst on a substrate. 5 The VI-SLS process, however, is complicated by high process temperatures that tend toward the formation of carbide and oxide phases that limit electrochemical capacity and rate capabilities.Electrospinning is a continuous nanofabrication technique based on the principle of electrohydrodynamics, 6,7 and is capable of producing nanowires of synthetic and natural polymers, ceramics, carbon, and semiconductor materials with the diameter in the range of 1-2000 nm. 8-10 While the Taylor cone instability associated with electrospinning was historically used for nozzle-based systems, the surface instability of thin films of soluble polymers in the presence of an electric field enabled the development of needleless electrospinning, whereby numerous jets spin coincidently allowing a continuous roll-to-roll manufacturing process. 11 This is in stark contrast to the two common SiNW preparation methods where the abilit...

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“…14 The same reaction occurred with an analogous tridentate ligand. 15,16 Thus, in the presence of a strong ligand, even a strong silicon-hydrogen bond can be cleaved, leading to disproportionation products.…”

Section: At 50mentioning

confidence: 99%

Studies on the disproportionation of trichloromethyltin

Bertelo¹,

Duriez

Girois³

et al. 2003

Applied Organom Chemis

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The rate of disproportionation of trichloromethyltin in various solvents was studied by two methods, derivatization with sodium tetraethylborate and 13 C NMR measurements, which gave similar results. The reaction followed second-order kinetics and was more rapid in coordinating solvents than in uncoordinating ones. Moreover, it was catalyzed by nucleophiles, such as amines or alcohols, which is in favor of a nucleophile-assisted electrophilic reaction.

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Amine-Promoted Disproportionation and Redistribution of Trichlorosilane: Formation of Tetradecachlorocyclohexasilane Dianion¹

Cited by 89 publications

References 10 publications

Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn–Teller effect

Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn–Teller effect

Si[sub 6]H[sub 12]/Polymer Inks for Electrospinning a-Si Nanowire Lithium Ion Battery Anodes

Studies on the disproportionation of trichloromethyltin

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Amine-Promoted Disproportionation and Redistribution of Trichlorosilane: Formation of Tetradecachlorocyclohexasilane Dianion1

Cited by 89 publications

References 10 publications

Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn–Teller effect

Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn–Teller effect

Si[sub 6]H[sub 12]/Polymer Inks for Electrospinning a-Si Nanowire Lithium Ion Battery Anodes

Studies on the disproportionation of trichloromethyltin

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Amine-Promoted Disproportionation and Redistribution of Trichlorosilane: Formation of Tetradecachlorocyclohexasilane Dianion¹