The Synthesis and Isolation of a Metal‐Substituted Bis‐silene

Bravo‐Zhivotovskii, Dmitry; Dobrovetsky, Roman; Nemirovsky, Dmitry; Molev, Victoria; Bendikov, Michael; Molev, Gregory; Botoshansky, Mark; Apeloig, Yitzhak

doi:10.1002/anie.200800973

Cited by 44 publications

(15 citation statements)

References 30 publications

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“…Moreover, a change from a migrating silyl group to a migrating germyl (stannyl) group weakens the O–E bond strength ( E O – E = Si > Ge > Sn), raising the energy of the silene (ON) side. Increased steric bulk of the migrating group should also disfavor the acylsilane (OFF) side as recently found by Bravo-Zhivotovskii et al 24 Finally, one can expect that increased conjugation, as found in the silenes studied herein, will lower the relative energies of these species. Our initial model species for the acylsilane/Brook-silene switches, together with their carbon analogues, are displayed in Scheme 2.…”

Section: Introductionsupporting

confidence: 74%

New Class of Molecular Conductance Switches Based on the [1,3]-Silyl Migration from Silanes to Silenes

et al. 2013

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On the basis of first-principles density functional theory calculations, we propose a new molecular photoswitch which exploits a photochemical [1,3]-silyl(germyl) shift leading from a silane to a silene (a Si=C double bonded compound). The silanes investigated herein act as the OFF state, with tetrahedral saturated silicon atoms disrupting the conjugation through the molecules. The silenes, on the other hand, have conjugated paths spanning over the complete molecules and thus act as the ON state. We calculate ON/OFF conductance ratios in the range of 10–50 at a voltage of +1 V. In the low bias regime, the ON/OFF ratio increases to a range of 200–1150. The reverse reaction could be triggered thermally or photolytically, with the silene being slightly higher in relative energy than the silane. The calculated activation barriers for the thermal back-rearrangement of the migrating group can be tuned and are in the range 108–171 kJ/mol for the switches examined herein. The first-principles calculations together with a simple one-level model show that the high ON/OFF ratio in the molecule assembled in a solid state device is due to changes in the energy position of the frontier molecular orbitals compared to the Fermi energy of the electrodes, in combination with an increased effective coupling between the molecule and the electrodes for the ON state.

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Section: Introductionsupporting

confidence: 74%

New Class of Molecular Conductance Switches Based on the [1,3]-Silyl Migration from Silanes to Silenes

et al. 2013

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“…In the case of C=Si, a mercury derivative has been reported. 69 As far as P=Si is concerned, zinc and iron derivatives are known. 70,71 The ease of synthesis is presumably the major reason why so far reactivity studies of disilenides have been predominantly centered on the derivatives 10 and 14a.…”

Section: ç Conclusion and Outlookmentioning

confidence: 99%

The Versatile Chemistry of Disilenides: Disila Analogues of Vinyl Anions as Synthons in Low-valent Silicon Chemistry

Scheschkewitz

2010

Chemistry Letters

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Since the first isolation of a disila analog to vinyl anion synthons, namely lithium disilenide Tip 2 Si=Si(Tip)Li (Tip: 2,4,6-triisopropylphenyl), the number of available disilenides and their synthetic applications have rapidly expanded. Derivatives with aryl, silyl, alkyl, and hydrogen substituents have been reported and even one cyclic derivative is available. Disilenides can be used to introduce the Si=Si unit to a variety of organic and inorganic substrates. Depending on whether products feature sufficiently reactive residual functionality, the Si=Si bond is either retained or undergoes further (so far intramolecular) transformations. Heteroatom-substituted disilenes are easily accessible via disilenides. Using Tip 2 Si=Si(Tip)Li as a starting material, for instance, a variety of otherwise inaccessible compounds can be prepared: conjugated systems with more than one Si=Si unit, © 1 -transition-metal complexes, functional homo-and heteronuclear silacycles, and molecular silicon clusters with substituent-free vertices. In this review article, an account on the chemistry of disilenides is given.

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“…Even though silenes are one of the cornerstones of low-coordinate silicon chemistry, the first and still only example of a stable metal-substituted derivative was reported by Bravo-Zhivotovskii and Apeloig et al only very recently. [25] The reaction of dilithiated bisA C H T U N G T R E N N U N G (silyl)mercury 9 a (Scheme 3) with adamantoyl chloride presumably yields the transient bis(acylsilyl) derivative 10 a, which spontaneously undergoes a double Brook rearrangement to the mercury-bridged bis-…”

Section: A Silenide (Si=c)mentioning

confidence: 99%

Anionic Reagents with Silicon‐Containing Double Bonds

Scheschkewitz

2009

Chemistry A European J

114

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E=Si transfer: Anionic compounds capable of transferring a silicon-containing double bond are reviewed (see figure), particularly reagents with Si=Si moieties (Tip=2,4,6-iPr(3)C(6)H(2), M=Li, Na, K) and their applications towards main-group and transition-metal electrophiles, as well as their reactivity towards organic compounds. A few recently reported derivatives with Si=C (Ad=1-adamantyl) and Si=P moieties are included for completeness.Anionic compounds capable of transferring a silicon double bond are summarized following an introduction to the differences between alkenes and their heavier homologues. The main focus is on reagents with Si=Si moieties and their applications towards main-group and transition-metal electrophiles, as well as their reactivity towards organic compounds, but a few recently reported derivatives with Si=C and Si=P bonds are also included.

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The Synthesis and Isolation of a Metal‐Substituted Bis‐silene

Cited by 44 publications

References 30 publications

New Class of Molecular Conductance Switches Based on the [1,3]-Silyl Migration from Silanes to Silenes

New Class of Molecular Conductance Switches Based on the [1,3]-Silyl Migration from Silanes to Silenes

The Versatile Chemistry of Disilenides: Disila Analogues of Vinyl Anions as Synthons in Low-valent Silicon Chemistry

Anionic Reagents with Silicon‐Containing Double Bonds

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