A Tricyclic Aromatic Isomer of Hexasilabenzene

@article{Abersfelder2010ATA,
  title={A Tricyclic Aromatic Isomer of Hexasilabenzene},
  author={Kai Abersfelder and Andrew J. P. White and Henry S. Rzepa and David Scheschkewitz},
  journal={Science},
  year={2010},
  volume={327},
  pages={564 - 566}
}
Aromatic Silicon Benzene has long intrigued chemists on account of the energy stabilization, termed aromaticity, which arises from π-electron delocalization around its ring framework. A persistent question has been how such stabilization would be impacted were the carbons to be replaced by heavier atoms such as silicon. Abersfelder et al. (p. 564) have prepared a benzene analog with Si atoms in place of all six-ring carbons, but a slightly altered bonding framework in which substituents outside… 

An experimental charge density study of two isomers of hexasilabenzene.

TLDR
The bonding situation in the ring (1) and cage isomer of hexasilabenzene (TipSi)6 is analyzed on the basis of experimental charge-density investigations and an analogous transformation for fully saturated silicon compounds under irradiative conditions has been described by Kira and co-workers.

σ-Aromaticity in an unsaturated ring: osmapentalene derivatives containing a metallacyclopropene unit.

TLDR
Reporting herein is an example of σ-aromaticity in an unsaturated three-membered ring (3 MR), which is supported by experimental observations and theoretical calculations and reveals the nature of ρ-arodicity in the unsaturated 3’MR.

A stable germanone as the first isolated heavy ketone with a terminal oxygen atom.

TLDR
It is reported that, with the first isolation of a monomeric germanium ketone analogue (Eind)(2)Ge=O), the germanone exhibits unique reactivities that are not observed with ordinary ketones, including the spontaneous trapping of CO(2) gas to provide a cyclic addition product.

Single-Crystal X-ray Structure of 1,3-Dimethylcyclobutadiene by Confinement in a Crystalline Matrix

TLDR
This work immobilizes a precursor, 4,6-dimethyl-α-pyrone, in a guanidinium-sulfonate-calixarene (G4C) crystalline network that confines the guest through a combination of CH-π and hydrogen-bond interactions, and supports experimental observation of square-planar and rectangular-bent geometries in the G4C host matrix.

A Planar Rhombic Charge-Separated Tetrasilacyclobutadiene

TLDR
The rhombic-shaped charge-separated singlet state of compound 1 thus stabilizes its cyclic 4π-electron antiaromaticity in a manner that contrasts sharply with the bond-length alternation, characterizing the rectangular distortion of carbon-based CBD.

σ-Aromaticity in a Fully Unsaturated Ring.

TLDR
A strong correlation between nucleus-independent chemical shift (NICS) values and extra cyclic resonance energies (ECREs) is demonstrated, which are used to evaluate the σ-aromaticity in an unsaturated three-membered ring of cyclopropene, which were computed by molecular orbital (MO) theory and valence bond (VB) theory, respectively.

π-Electron systems containing Si=Si double bonds

TLDR
This review focuses on the recent advances in the chemistry of π-electron systems containing Si=Si double bonds, mainly published in the last decade, and the synthesis, characterization, and potential application of a variety of donor-free ρ-conjugated disilene compounds.

Synthesis of a pentasilapropellane. Exploring the nature of a stretched silicon-silicon bond in a nonclassical molecule.

TLDR
Reactivity studies provide evidence for both closed-shell and radical-type reactivity, confirming the unusual nature of the stretched silicon-silicon bond in this "nonclassical" molecule.

Electron-Deficiency Aromaticity in Silicon Nanoclusters.

  • H. Vach
  • Chemistry
    Journal of chemical theory and computation
  • 2012
TLDR
This work exploits the natural tendency of silicon toward overcoordination to construct electron-deficient molecules with ring structures that are more stable than any other known hydrogenated silicon nanoparticles of this size and exhibit aromatic-like properties due to strong electron delocalization.

A stable heavier group 14 analogue of vinylidene.

TLDR
It is shown that by employing the bulky and strongly electron-donating boryl ligand (HCDippN)2B (Dipp, 2,6-iPr2C6H3), a simple monomeric digermavinylidene compound, (boryl)2GeGe, can be synthesized and is stable at room temperature.
...

References

SHOWING 1-10 OF 37 REFERENCES

Aromaticity of group 14 organometallics: experimental aspects.

TLDR
The current state of affairs in the chemistry of aromatic compounds of the heavier Group 14 elements, the latest experimental achievements, as well as future prospects in the field are discussed.

Chiral Aromaticities. A Topological Exploration of Möbius Homoaromaticity.

TLDR
It is suggested that the ELF and ELFπ thresholds for any basin found in the homoregion are better indicators of the delocalized nature of the homoaromatic interaction and the aromaticity of the system.

Hexasilabenzene (Si6H6). Is the benzene-like D6h structure stable?

Ab initio molecular orbital theory has been applied to the structure of hexasilabenzene (Si6H6), the silicon analog of benzene (C6H6). The minimum energy structure is calculated to be planar with D6h

Lone Pair Functionality in Divalent Lead Compounds

The role of the lone pair of electrons of Pb(II) in determining the coordination geometry is analyzed from crystallographic studies and ab initio molecular orbital optimizations. Of particular

A Stable Compound Containing a Silicon-Silicon Triple Bond

The reaction of 2,2,3,3-tetrabromo-1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasilane with four equivalents of potassium graphite (KC8) in tetrahydrofuran produces

The Silabenzenes: Structure, Properties, and Aromaticity

The electronic structure and properties of the silabenzenes series have been investigated using basis sets of spdf quality and many-body perturbation theory, hybrid density functional theory, and

Progress in the Chemistry of Stable Disilenes

Publisher Summary Remarkable progress of the chemistry of disilenes seems to encourage building up the modern general theory of bonding, structure, and reactions applied for the heavier main-group

Exploration of C6H6 Potential Energy Surface: A Computational Effort to Unravel the Relative Stabilities and Synthetic Feasibility of New Benzene Isomers†

Ab initio (MP2, CCSD(T)) and hybrid density functional theory (B3LYP) calculations with up to triple-ζ basis set were done to locate all possible minima, where each carbon in the molecule is

Homoconjugation/homoaromaticity in main group inorganic molecules.

TLDR
Quantum chemical computations show that three groups of inorganic ions and neutral molecules are aromatic due to through-space homoconjugation, including the spherically homoaromatic Te(6)(4+), and the diamagnetic (O(2))(4) structural unit recently observed in epsilon-phase oxygen solid has quadruple PTS-like aromaticity.

Syntheses of trisila analogues of allyl chlorides and their transformations to chlorocyclotrisilanes, cyclotrisilanides, and a trisilaindane.

TLDR
The X-ray diffraction studies on single crystals of 6a,b and 7b reveal that the Si-Si bond distance in cyclotrisilanes depends significantly on the electronegativity of the opposing silicon atom's substituents, which is rationalized by density functional theory (DFT) calculations on model systems.