Tetrasupersilyl-tristannaallene and -tristannacyclopropene (tBu3Si)4Sn3 – Isomers with the Shortest Sn=Sn Double Bonds to Date

Wibeŕg, Nils; Lerner, Hans‐Wolfram; Vasisht, Sham Kumar; Wagner, S.; Karaghiosoff, Konstantin; Nöth, Heinrich; Ponikwar, Werner

doi:10.1002/(sici)1099-0682(199908)1999:8<1211::aid-ejic1211>3.0.co;2-0

Cited by 120 publications

(15 citation statements)

References 28 publications

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“…The few examples of the stable sila- and germaaromatic compounds reported recently by Tokitoh's group, which formally have the SiC (or GeC) fragments incorporated in benzene (or naphthalene) rings, also will not be covered in this review, since they belong to the class of heavy aromatics rather than heavy alkenes. The heavy allenes (silaallenes and germaallenes) with cumulated ECC double bonds (E = Si, Ge) also constitute an independent class of compounds, whose chemistry was recently thoroughly reviewed by Escudié, , and therefore will be outside the framework of the present review.…”

Section: Introductionmentioning

confidence: 99%

Heteronuclear Heavy Alkenes EE‘ (E, E‘ = Group 14 Elements): Germasilenes, Silastannenes, Germastannenes...Next Stop?

2004

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Recent advances in the chemistry of stable heteronuclear heavy alkenes >EdE′< (E, E′ ) group 14 elements) are reviewed, covering silenes (>SidC<), germenes (>GedC<), stannenes (>SndC<), germasilenes (>GedSi<), silastannenes (>SidSn<), and germastannenes (>GedSn<). Their unique structures, bonding modes, and reactivities have been shown to be different from those of the homonuclear species, primarily due to the polarity of the >EdE′< bond resulting from the difference in the electronegativities of the doubly bonded atoms.

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Section: Introductionmentioning

confidence: 99%

Heteronuclear Heavy Alkenes EE‘ (E, E‘ = Group 14 Elements): Germasilenes, Silastannenes, Germastannenes...Next Stop?

2004

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“…Subsequently, Int produces cyclic isomer 2 via TS2. Other forms of thermal isomerization that give the corresponding three-membered rings of tetrasilyl-substituted trisilaallene 23 and tristannaallene 24 have also been reported. These products arise from the large contribution of the metallylene-substituted vinylidenes heavier analogues.…”

Section: Electronic Structure Ofmentioning

confidence: 95%

A linear C=Ge=C heteroallene with a di-coordinated germanium atom

Sugamata

Asakawa

Hashizume

et al. 2023

Preprint

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Allenes (>C=C=C<) are classified as cumulated dienes that have a linear structure with an sp-hybridized central carbon atom. We have succeeded in synthesizing and isolating a stable 2-germapropadiene derivative with bulky silyl substituents. The 2-germapropadiene allene moiety adopts a linear structure both in the solid state and in solution. In addition, an X-ray diffraction electron-density-distribution analysis of this 2-germapropadiene revealed a linear C=Ge=C geometry with a formally sp-hybridized germanium atom bearing two orthogonal C=Ge pi-bonds. Based on detailed structural and computational studies, it can be concluded that the linear geometry of the isolated 2-germapropadiene most likely arises from the negative hyperconjugation of the silyl substituents at the terminal carbon atoms. The 2-germapropadiene reacts rapidly with nucleophiles, indicating that the linearly oriented germanium atom is highly electrophilic.

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“…It should be mentioned that the synthesis of Sn 0 complexes is especially difficult due to their intrinsic lability, readily giving free ligands and elemental tin. To date, besides the tristannaallene reported by Wiberg and co-workers in 1999, only two other Sn 0 complexes supported by multidentate ligands are known. , Compound 35 represents a genuine isolable stannylone stabilized only by a bidentate bis(NHSi) ligand.…”

Section: Bis(silylene)-ligated Sn0 Complexesmentioning

confidence: 96%

Chelating Bis-silylenes As Powerful Ligands To Enable Unusual Low-Valent Main-Group Element Functions

et al. 2023

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Metrics & More Article Recommendations CONSPECTUS: Silylenes are divalent silicon species with an unoccupied 3p orbital and one lone pair of electrons at the Si II center. Owing to the excellent σ-donating ability of amidinatobased silylenes, which stems from the intramolecular imino-N donor interaction with the vacant 3p orbital of the silicon atom, Nheterocyclic amidinato bis(silylenes) [bis(NHSi)s] can serve as versatile strong donating ligands for cooperative stabilization of central atoms in unusually low oxidation states. Herein, we present our recent achievement on the application of bis(NHSi) ligands with electronically and spatially different spacers to main-group chemistry, which has allowed the isolation of a variety of low-valent compounds consisting of monatomic zero-valent group 14 E 0 complexes (named "metallylones", E = Si, Ge, Sn, Pb); monovalent group 15 E I complexes (E = N, P, isoelectronic with metallylones); and diatomic low-valent E 2 complexes (E = Si, Ge, P) with intriguing electronic structures and chemical reactivities. The role of the Si II •••Si II distance was revealed to be crucial in this chemistry. Utilizing the pyridine-based bis(NHSi) (Si•••Si distance: 7.8 Å) ligand, germanium(0) complexes with additional Fe(CO) 4 protection at the Ge 0 site have been isolated. Featuring a shorter Si•••Si distance of 4.3 Å, the xanthene-based bis(NHSi) has allowed the realization of the full series of heavy zero-valent group 14 element E 0 complexes (E = Si, Ge, Sn, Pb), while the o-carborane-based bis(NHSi) (Si•••Si distance: 3.3 Å) has enabled the isolation of Si 0 and Ge 0 complexes. Remarkably, reduction of the o-carborane-based bis(NHSi)-supported Si 0 and Ge 0 complexes induces the movement of two electrons into the o-carborane core and provides access to Si I −Si I and Ge I −Ge I species as oxidation products. Additionally, the o-carborane-based bis(NHSi) reacts with adamantyl azide, leading to a series of nitrogen(I) complexes as isoelectronic species of a carbone (C 0 complex). Moreover, cooperative activation of white phosphorus gives bis(NHSi)-supported phosphorus complexes with varying and unexpected electronic structures when employing the xanthene-, o-carborane-, and anilinebased bis(NHSi)s. With the better kinetic protection provided by the xanthene-based bis(NHSi), small-molecule activation and functionalization of the bis(NHSi)-supported central E or E 2 atoms (E = Si, Ge, P) are possible and furnish several novel functionalized silicon, germanium, and phosphorus compounds.With knowledge of the ability of chelating bis(NHSi)s in coordinating and functionalizing low-valent group 14 and 15 elements, the application of these ligand systems to other main-group elements such as group 2 and 13 is quite promising. To fully understand the role of the NHSi in a bis(NHSi) ligand, introducing a mixed ligand, i.e., the combination of an NHSi with other functional groups, such as Lewis acidic borane or Lewis basic borylene, in one chelating ligand could lead to new types of low-valent main-...

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Tetrasupersilyl-tristannaallene and -tristannacyclopropene (tBu3Si)4Sn3 – Isomers with the Shortest Sn=Sn Double Bonds to Date

Cited by 120 publications

References 28 publications

Heteronuclear Heavy Alkenes EE‘ (E, E‘ = Group 14 Elements): Germasilenes, Silastannenes, Germastannenes...Next Stop?

Heteronuclear Heavy Alkenes EE‘ (E, E‘ = Group 14 Elements): Germasilenes, Silastannenes, Germastannenes...Next Stop?

A linear C=Ge=C heteroallene with a di-coordinated germanium atom

Chelating Bis-silylenes As Powerful Ligands To Enable Unusual Low-Valent Main-Group Element Functions

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