Journal ArticleDOI
A stable silicon-based allene analogue with a formally sp -hybridized silicon atom
TLDR
The synthesis of a thermally stable, crystalline trisilaallene derivative containing a formally sp-hybridized silicon atom is reported, and it is found that, in contrast to linear carbon allenes, the tristannaallene is significantly bent.Abstract:
Carbon chemistry exhibits a rich variety in bonding patterns, with homo- or heteronuclear multiple bonds involving sp-hybridized carbon atoms as found in molecules such as acetylenes, nitriles, allenes and carbon dioxide. Carbon's heavier homologues in group 14 of the periodic table—including silicon, germanium and tin—were long thought incapable of forming multiple bonds because of the less effective pπ–pπ orbital overlap involved in the multiple bonds. However, bulky substituents can protect unsaturated bonds and stabilize compounds with formally sp-hybridized heavy group-14 atoms1,2: stable germanium2, tin3 and lead4 analogues of acetylene derivatives and a marginally stable tristannaallene5 have now been reported. However, no stable silicon compounds with formal sp-silicon atoms have been isolated. Evidence for the existence of a persistent disilaacetylene6 and trapping7 of transient 2-silaallenes and other X = Si = X′ type compounds (X, X′ = O, CR2, NR, and so on) are also known, but stable silicon compounds with formally sp-hybridized silicon atoms have not yet been isolated. Here we report the synthesis of a thermally stable, crystalline trisilaallene derivative containing a formally sp-hybridized silicon atom. We find that, in contrast to linear carbon allenes, the trisilaallene is significantly bent. The central silicon in the molecule is dynamically disordered, which we ascribe to ready rotation of the central silicon atom around the molecular axis.read more
Citations
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Journal ArticleDOI
π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium
Roland Fischer,Philip P. Power +1 more
TL;DR: The key unifying feature of almost all molecules discussed in this review is that they are generally stabilized by the use of bulky substituents which block associative or various decomposition pathways.
Journal ArticleDOI
Stable singlet carbenes as mimics for transition metal centers
TL;DR: This perspective summarizes recent results, which demonstrate that stable carbenes can activate small molecules and stabilize highly reactive intermediates and main group elements in the zero oxidation state and paramagnetic species.
Journal ArticleDOI
Synthesis of an Extremely Bent Acyclic Allene (A “Carbodicarbene”): A Strong Donor Ligand
TL;DR: It is reasoned that weakening the p bonds of all-carbon allenes A1 should make them more flexible, and ultimately lead to a bending of the otherwise rigid and linear C=C=C skeleton, and it is shown that bent allenes should not be considered as laboratory curiosities, but instead a novel class of strong h-donor ligands for transition-metal centers.
Journal ArticleDOI
Oxidative Addition and Reductive Elimination at Main-Group Element Centers
Terry Chu,Georgii I. Nikonov +1 more
TL;DR: This Review highlights the substantial progress achieved in the past decade for the activation of robust single bonds by main-group compounds and the more recently realized activation of multiple bonds by these elements.
Journal ArticleDOI
A Brief Survey of Our Contribution to Stable Carbene Chemistry
TL;DR: This personal account summarizes the work, beginning with the discovery of the first stable carbene in 1988 up until the recent isolation of mesoionic carbenes, showing that these stable species are not limited to the role of ligand for transition metals, but that they are also powerful agents for the activation of small molecules, and for the stabilization of highly reactive diamagnetic and paramagnetic species.
References
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The First Isolable Dialkylsilylene
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Synthesis and Characterization of 2,6-Trip2H3C6PbPbC6H3-2,6-Trip2 (Trip = C6H2-2,4,6-i-Pr3): A Stable Heavier Group 14 Element Analogue of an Alkyne
TL;DR: The Stable Heavier Group 14 Element Analogue of an Alkyne (SHE 14) as discussed by the authors is a stable heavier group 14 analogue of an alkyne.
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Synthesis and characterization of a digermanium analogue of an alkyne.
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Synthesis and Characterization of 2,6-Dipp2-H3C6SnSnC6H3-2,6-Dipp2 (Dipp = C6H3-2,6-Pri2): A Tin Analogue of an Alkyne
TL;DR: In this article, the reaction of Sn(Cl)C6H3-2,6-Dipp2 with a stoichiometric amount of potassium in benzene has been investigated.
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Invisible but Common Motion in Organic Crystals: A Pedal Motion in Stilbenes and Azobenzenes
Jun Harada,Keiichiro Ogawa +1 more
TL;DR: The results demonstrated that the pedal motion should always be taken into account, even if no disorder is detected, in dynamic processes of (E)-stilbene and (E-3,3',4,4'-tetramethylazobenzene in crystals.