Disilene–Silylene Interconversion: A Synthetically Accessible Acyclic Bis(silyl)silylene

Reiter, Dominik; Holzner, Richard; Porzelt, Amelie; Altmann, Philipp J.; Frisch, Philipp; Inoue, Shigeyoshi

doi:10.1021/jacs.9b05318

Cited by 73 publications

(72 citation statements)

References 104 publications

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“…The π‐donating substituents (amido or NHI ligands) in silylenes 14 , 15 , and 37a lead to a decreased HOMO–LUMO gap [2.04 eV ( 14 ), 1.99 eV ( 15 ), 2.96 eV ( 37a )], which allows for the activation of inert molecules. Furthermore, the disilene 41 /silylene 40 equilibrium mixture was also found to activate H 2 under very mild conditions (–40 °C) . Interestingly, the HOMO–LUMO energy gap in the singlet bis(silyl)silylene 40 (4.18 eV) is comparably larger than those of acyclic silylenes, which are able to activate H 2 , and similar to those of acyclic silylenes 17a (4.26 eV) and 21 (4.33 eV), which have shown no reaction toward H 2 .…”

Section: Small Molecule Activation With Acyclic Silylenesmentioning

confidence: 85%

“…Our group also presented an isolable bis(silyl)silylene 40 which is in equilibria with the corresponding tetrasilyldisilene 41 . The reaction of dibromosilane {(TMS) 3 Si}( t Bu 3 Si)SiBr 2 ( 39 ) with KC 8 afforded an equilibrium mixture of 40 and 41 (Scheme ) . These compounds 38 and 41 can behave as synthetic alternatives to acyclic silylenes.…”

Section: Synthesismentioning

confidence: 99%

“…Silylenes are well known to undergo cycloaddition reactions with unsaturated C–C bonds , . Similarly, silylenes 21 , 37a , and 40 reacted with ethylene under mild conditions (1 atm, r.t.) to form the corresponding cycloaddition products 56 , 59 , and 60 (Scheme ) , , . In the case of silylene 15 , the reaction with ethylene at ambient temperatures gave the silirane product Si{CH 2 –CH 2 }{NDipp(SiMe 3 )}{Si(SiMe 3 ) 3 } ( 57 ) in high yields.…”

Section: Small Molecule Activation With Acyclic Silylenesmentioning

confidence: 99%

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Small Molecule Activation by Two‐Coordinate Acyclic Silylenes

Fujimori

Inoue

2020

Eur J Inorg Chem

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In recent decades, the chemistry of stable silylenes (R2Si:) has evolved significantly. The first major development in this chemistry was the isolation of a silicocene which is stabilized by the Cp* (Cp* = η5‐C5Me5) ligand in 1986 and subsequently the isolation of a first N‐heterocyclic silylene (NHSi:) in 1994. Since the groundbreaking discoveries, a large number of isolable cyclic silylenes and higher coordinated silylenes, i.e. Si(II) compounds with coordination number greater than two, have been prepared and the properties investigated. However, the first isolable two‐coordinate acyclic silylene was finally reported in 2012. The achievements in the synthesis of acyclic silylenes have allowed for the utilization of silylenes in small molecule activation including inert H2 activation, a process previously exclusive to transition metals. This minireview highlights the developments in silylene chemistry, specifically two‐coordinate acyclic silylenes, including experimental and computational studies which investigate the extremely high reactivity of the acyclic silylenes.

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Section: Small Molecule Activation With Acyclic Silylenesmentioning

confidence: 85%

Section: Synthesismentioning

confidence: 99%

Section: Small Molecule Activation With Acyclic Silylenesmentioning

confidence: 99%

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Small Molecule Activation by Two‐Coordinate Acyclic Silylenes

Fujimori

Inoue

2020

Eur J Inorg Chem

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“…Silylenes, i.e., divalent silicon analogues of carbenes, represent highly attractive reactive intermediates due to their considerable potential as building blocks for organosilicon compounds [1][2][3][4][5][6][7]. There are several examples of stable silylenes, which are usually stabilized thermodynamically by introduction of heteroatom-based substituents such as amino groups.…”

Section: Introductionmentioning

confidence: 99%

“…In this context, easily accessible and bottleable precursors for carbon-substituted silylenes would be an attractive research target. In most cases, silylenes can be generated by reduction of a dihalosilane or photolysis of a trisilane [4,7,33]. When the substituents on the central silicon atom offer insufficient steric protection, the products from the aforementioned reactions usually afford complex mixtures of oligosilanes.…”

Section: Introductionmentioning

confidence: 99%

Generation of Bis(ferrocenyl)silylenes from Siliranes

et al. 2020

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Divalent silicon species, the so-called silylenes, represent attractive organosilicon building blocks. Isolable stable silylenes remain scarce, and in most hitherto reported examples, the silicon center is stabilized by electron-donating substituents (e.g., heteroatoms such as nitrogen), which results in electronic perturbation. In order to avoid such electronic perturbation, we have been interested in the chemistry of reactive silylenes with carbon-based substituents such as ferrocenyl groups. Due to the presence of a divalent silicon center and the redox-active transition metal iron, ferrocenylsilylenes can be expected to exhibit interesting redox behavior. Herein, we report the design and synthesis of a bis(ferrocenyl)silirane as a precursor for a bis(ferrocenyl)silylene, which could potentially be used as a building block for redox-active organosilicon compounds. It was found that the isolated bis(ferrocenyl)siliranes could be a bottleable precursor for the bis(ferrocenyl)silylene under mild conditions.

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Low Valent Main Group Compounds in Small Molecule Activation

Weetman

2021

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Since the discovery that main group elements can mimic transition metals, efforts have focussed on harnessing main group elements' abilities to break strong bonds to enable new sustainable methodologies. In this regard, use of small molecules, such as those found in greenhouse gases, is a prime target for incorporation into catalytic cycles to produce value‐added products. Initial challenges in main group chemistry focussed on the ability to isolate these highly reactive low‐oxidation state species, whilst also maintaining the reactive sites. An array of low valent compounds have been successfully isolated (i.e., multiple bonds, tetrylenes, anions, and cations), through careful ligand design, and have challenged traditional bonding models and preconceptions of the main group elements. Current advances have highlighted how reactive these low‐valent sites are with the ability to activate strong bonds, such as those found in small molecules (e.g., H 2 , CO, CO 2 , etc.). This represents the first step in a redox‐based catalytic cycle, as the low‐valent main group center undergoes oxidative addition reactions. Current challenges remain in reductive elimination, and thus functionalization of the small molecule, but examples of low‐valent main group elements in catalysis are starting to emerge and represent a bright future for main group chemistry. This article highlights the achievements of low valent main group elements, with a focus on group 2, 13, and 14 elements, in small molecule activation as well as the fundamental concepts that have aided the development of this rapidly advancing field.

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Disilene–Silylene Interconversion: A Synthetically Accessible Acyclic Bis(silyl)silylene

Cited by 73 publications

References 104 publications

Small Molecule Activation by Two‐Coordinate Acyclic Silylenes

Small Molecule Activation by Two‐Coordinate Acyclic Silylenes

Generation of Bis(ferrocenyl)silylenes from Siliranes

Low Valent Main Group Compounds in Small Molecule Activation

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