Properties and applications of polysilanes

Kumar, Vipin; Leitao, Erin M.

doi:10.1002/aoc.5402

Cited by 40 publications

(23 citation statements)

References 140 publications

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“…Cyclic oligosilanes, silicon compounds with two or three-dimensional frameworks such as cage-, polyhedron-, ladder-, bowl-, and sphere-shaped structures, exhibit the electronic structures due to the σ conjugation depending on their fixed conformation − and should be potential units for large σ conjugated systems. − Such cyclic oligosilanes have recently been demonstrated as units for judiciously designed molecular wires that can be conductive materials and molecular electronic devices. − To increase the diversity of the structures and properties of highly ordered silicon materials based on the cyclic oligosilanes, development of the efficient condensation reactions of cyclic oligosilanes to form Si–Si bonds under milder conditions remains crucial. Various silicon skeletons are generally synthesized through the following reactions: the metathesis of halosilanes or alkoxysilanes with metal silanides, the Wurtz-type coupling reactions of halosilanes, the disproportionation reactions of polyhalogenated silanes with chloride ion, ,− the rearrangement of polymethyloligosilanes with aluminum trichloride, − the dehydrogenative coupling reaction of di- or trihydrosilanes, and the living polymerization of masked disilenes .…”

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confidence: 99%

One-Pot Condensation of a Bicyclo[1.1.1]pentasilane through Elimination of Iodotrimethylsilane Assisted by a Lewis Base

Yokouchi

Iwamoto

2020

Organometallics

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Development of efficient bond formation reactions remains important in organic and main-group-element chemistry. Herein, we report the metal-free one-pot condensation reaction of 1iodo-3-trimethylsilyl-substituted bicyclo[1.1.1]pentasilane (BPS) in the presence of 4-(dimethylamino)pyridine (DMAP) providing oligomers of BPS, persila[n]staffanes (n = 2, 3), which involves the successive Si−Si bond formation reaction accompanied by the concomitant formation of iodotrimethylsilane (TMSI) in the form of a DMAP complex. The computational study suggests that the formation of a pentasila[1.1.1]propellane−DMAP complex resulting from the elimination of TMSI from the BPS is a key intermediate.

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confidence: 99%

One-Pot Condensation of a Bicyclo[1.1.1]pentasilane through Elimination of Iodotrimethylsilane Assisted by a Lewis Base

Yokouchi

Iwamoto

2020

Organometallics

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“…Outside of biology, chiral polysilanes are of interest to polymer chemists. 92 Polysilanes are polymers containing solely silicon backbones, and this σ-conjugated backbone endows these molecules with unique electronic and optical properties. When their backbone Si atoms are connected to chiral side groups, the resulting chiral polysilanes form helical structures.…”

Section: Opportunities For Biocatalysis To Impact Organosilicon Chemistrymentioning

confidence: 99%

“…Outside of biology, chiral polysilanes are of interest to polymer chemists . Polysilanes are polymers containing solely silicon backbones, and this σ-conjugated backbone endows these molecules with unique electronic and optical properties.…”

Section: Opportunities For Biocatalysis To Impact Organosilicon Chemi...mentioning

confidence: 99%

Biocatalytic Transformations of Silicon—the Other Group 14 Element

et al. 2021

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Significant inroads have been made using biocatalysts to perform new-to-nature reactions with high selectivity and efficiency. Meanwhile, advances in organosilicon chemistry have led to rich sets of reactions holding great synthetic value. Merging biocatalysis and silicon chemistry could yield new methods for the preparation of valuable organosilicon molecules as well as the degradation and valorization of undesired ones. Despite silicon’s importance in the biosphere for its role in plant and diatom construction, it is not known to be incorporated into any primary or secondary metabolites. Enzymes have been found that act on silicon-containing molecules, but only a few are known to act directly on silicon centers. Protein engineering and evolution has and could continue to enable enzymes to catalyze useful organosilicon transformations, complementing and expanding upon current synthetic methods. The role of silicon in biology and the enzymes that act on silicon-containing molecules are reviewed to set the stage for a discussion of where biocatalysis and organosilicon chemistry may intersect.

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“…Although alkyl and phenyl substituents are quite benign from a chemical point of view, they are particularly promising because they are realistic synthetical targets for silicon and germanium based molecular cores. [49][50][51][52][53][54][55][56][57] We hope these results will motivate studies of the properties of substituted cyclic and bicyclic silanes and germanes. The transmission suppression is less clear in the C222 systems than for the silanes and germanes.…”

Section: Manuscriptmentioning

confidence: 99%

Substituent Control of σ-interference Effects in the Transmission of Saturated Molecules

Garner

Koerstz

Jensen

et al. 2021

Preprint

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The single-molecule conductance of saturated molecules can potentially be fully suppressed by destructive quantum interference in their σ-system. However, only few molecules with σ-interference have been identified and the structure-property relationship remains to be elucidated. Here, we explore the role of substituents in modulating the electronic transmission of saturated molecules. In functionalized bicyclo[2.2.2]octanes, the transmission is suppressed by σ- interference when fluorine substituents are applied. For bicyclo[2.2.2]octasilane and - octagermanes the transmission is suppressed when carbon-based substituents are used, and such molecules are likely to be highly insulating. For the carbon-based substituents we find a strong correlation between the appropriate Hammett constants and the transmission. The substituent effect enables systematic optimization of the insulating properties of saturated molecular cores.

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Properties and applications of polysilanes

Abstract: This review article presents an overview of the unique properties of polysilanes, attributed mainly to the existence of σ‐conjugation along the all‐silicon backbone. The most recent and exciting applications of polysilanes will also be highlighted.

Cited by 40 publications

References 140 publications

One-Pot Condensation of a Bicyclo[1.1.1]pentasilane through Elimination of Iodotrimethylsilane Assisted by a Lewis Base

One-Pot Condensation of a Bicyclo[1.1.1]pentasilane through Elimination of Iodotrimethylsilane Assisted by a Lewis Base

Biocatalytic Transformations of Silicon—the Other Group 14 Element

Substituent Control of σ-interference Effects in the Transmission of Saturated Molecules

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