An Unsaturated α,ω‐Dianionic Oligosilane

Abersfelder, Kai; Güclü, Deniz; Scheschkewitz, David

doi:10.1002/anie.200503975

Cited by 49 publications

(23 citation statements)

References 47 publications

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“…As proposed by the authors, irradiation as well appears to result in the Si=Si bond dissociation of one of the Si=Si double bonds in 37 to give the transient disilenyl silylene 40 and the Kira silylene [CH 2 C(SiMe 3 ) 2 ] 2 Si:, which is known to ring‐expand benzene to 41 via its excited state generated during photolysis . Similar reactions have been reported for stable and transient silylenes …”

Section: Si=si Transfer Reactionssupporting

confidence: 59%

Functional Disilenes in Synthesis

Rammo

Scheschkewitz

2018

Chemistry A European J

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Section: Si=si Transfer Reactionssupporting

confidence: 59%

Functional Disilenes in Synthesis

Rammo

Scheschkewitz

2018

Chemistry A European J

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“…The unperturbed Si=Si bond length of 219.8 pm and the absence of a red-shift of the longest wavelength UV-vis absorption at 415 nm in comparison to 1 implies that no significant charge delocalization is active in 10. The formal presence of two negative charges in the trisilendiide moiety of 10 and the resulting Coulomb repulsion served as rationalization of these findings [24].…”

Section: A Dichlorosilyl Disilene and A Trisilendiidementioning

confidence: 95%

“…To increase the number of functional groups available to this end, we investigated the reactivity of 1 toward trichloro silanes. Indeed, reaction of 1 with TipSiCl 3 afforded the dichlorosilyl disilene 9 (Scheme 6) [24].…”

Section: A Dichlorosilyl Disilene and A Trisilendiidementioning

confidence: 99%

“…Reaction of 10 with Me 2 SnCl 2 afforded the four-membered unsaturated heterocyclic silane 11, which, in the absence of information on its solid-state structure, was identified by multinuclear NMR spectroscopy, taking particular advantage of its diagnostic 117/119 Sn/ 29 Si coupling patterns [24]. Formation of 11 can be regarded as proof-of-principle for the suitability of 10 for the expansion of the unsaturated scaffold based on heavier group 14 elements by employment of the residual functionality.…”

Section: A Dichlorosilyl Disilene and A Trisilendiidementioning

confidence: 99%

“…3, pp. 595-602, 2010Homo-and heterocyclic silanes via Si=Si 599 Scheme 6 Synthesis of dichlorosilyl disilene 9, its reduction to the magnesium salt of a trisilendiide 10 and derivatization of 10 to the tin-containing unsaturated heterocyclic silane 11 (Tip = 2,4,6-i Pr 3 C 6 H 2 )[24].…”

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Synthesis of homo- and heterocyclic silanes via intermediates with Si=Si bonds

Abersfelder

Scheschkewitz

2010

Pure and Applied Chemistry

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An account is given of our efforts in the synthesis of homo-and heterocyclic silanes via occasionally stable unsymmetrically substituted disilene intermediates of the A 2 Si=Si(A)B type that are accessible from a disila analog of a vinyl lithium. This approach is particularly powerful in the preparation of three-membered rings such as cyclotrisilanes with a residual functionality that can be either electro-or nucleophilic in nature and can even give rise to ring-expanded products with preserved Si=Si moiety. The intermediacy of transient silylenes in some of these transformations is discussed as well as the structural effects of the electronic properties of the residual functional group. The relevance of these studies for the understanding of Si(100) surface annealed species during the epitaxial growth of elemental silicon is pointed out, and the potential of the methodology for the synthesis of unusual polycyclic silicon clusters is noted.

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Main‐Group Rings, Chains, and Polymer Compounds

Rabanzo-Castillo

Leitao

2017

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Although research in the field of main‐group rings, chains, and polymers is a less mature area of chemistry than that of carbon‐based rings, chains, and polymers, it is currently very fertile, as evidenced by the significant increase in available monocyclic main‐group rings in the past two decades, including neutral, anionic, cationic, and radical homocycles and heterocycles. Furthermore, recent advances in main‐group polymer chemistry have been substantial with access to high‐molecular‐weight polyaminoboranes and polyphosphinoboranes enabled by efficient dehydropolymerization catalysts, as well as the production of advanced cross‐linked polysulfide materials. Facile preparation and stabilization of low coordinate main‐group centers, synthesis of new reactive main‐group precursors, and the development of new routes to link main‐group elements together have been keys in moving the field forward. The scope of main‐group complexes has increased drastically, with multiple routes available to access the compounds, enabling a wide range of derivatives possible. In addition, compared to the carbon‐based systems, main‐group compounds feature more bonding options due to the different electronics and sterics afforded by the noncarbon atom(s) and, therefore, modified reactivity. As a result, existing theories such as aromaticity are challenged when new main‐group cycles are created. In this article, the most common routes to prepare the different types of main‐group rings, chains, and polymers are summarized, along with selected classic examples and recent additions to the field from across the p‐block (Groups 13–16). Both homonuclear and heteronuclear systems are covered, and some relevant information on characterization, properties, and uses of the compounds is also included.

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An Unsaturated α,ω‐Dianionic Oligosilane

Cited by 49 publications

References 47 publications

Functional Disilenes in Synthesis

Functional Disilenes in Synthesis

Synthesis of homo- and heterocyclic silanes via intermediates with Si=Si bonds

Main‐Group Rings, Chains, and Polymer Compounds

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