The Quest for Stable Silaaldehydes: Synthesis and Reactivity of a Masked Silacarbonyl

Sarkar, Debotra; Nesterov, V. I.; Szilvási, Tibor; Altmann, Philipp J.; Inoue, Shigeyoshi

doi:10.1002/chem.201805604

Cited by 37 publications

(32 citation statements)

References 56 publications

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“…The silicon center in 3 adopts a distorted tetrahedral geometry with a short Si−O distance of 1.557(4) and 1.537(4) Å in accordance with related four‐coordinated Lewis acid stabilized silanones (1.531–1.579 Å) containing a Si=O double bond . The Si−O distance is only slightly elongated when compared with recently reported genuine silanones (1.518–1.537 Å) .…”

Section: Methodssupporting

confidence: 77%

“…reported also the silaformyl chloride complex C , resulting from an NHC‐stabilized silylene and H 2 O⋅B(C 6 F 5 ) 3 . In 2019, the isolation of the first donor–acceptor‐supported silaaldehyde D was accomplished by the Inoue group . Remarkably, Kippings dream of isolable genuine silanones was realized in 2014 with the isolation of the first metallosilanone by Filippou and 2017 by the groups of Inoue and Rieger .…”

Section: Methodsmentioning

confidence: 99%

“…[14] In 2019, the isolation of the first donor-acceptor-supported silaaldehyde D was accomplished by the Inoue group. [15] Remarkably,K ippings dream of isolable genuine silanones was realized in 2014 with the isolation of the first metallosilanoneb yF ilippou [16] and 2017 by the groupso fI noue and Rieger. [17] Very recently,asilicon analogue of ak etone with an unperturbed Si=Ob ond was synthesized by Iwamoto and coworkers.…”

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confidence: 99%

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An Isolable Bis(Silanone–Borane) Adduct

Luecke

Pens

Yao

et al. 2020

Chemistry A European J

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The reaction of bis(silylenyl)‐substituted ferrocene 1 with two molar equivalents of BPh3 yields the corresponding bis(silylene–borane) Lewis adduct 2. The latter is capable to activate CO2 to furnish the borane‐stabilized bis(silanone) 3 through mono‐oxygenation of the dative SiII→B silicon centers under release of CO. Removal of BPh3 from 3 with PMe3 affords the corresponding 1,3,2,4‐cyclodisiloxane and the Me3P−BPh3 adduct. All isolated new compounds were characterized and their molecular structures were determined by single‐crystal X‐ray diffraction analyses.

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Section: Methodssupporting

confidence: 77%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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An Isolable Bis(Silanone–Borane) Adduct

Luecke

Pens

Yao

et al. 2020

Chemistry A European J

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“…Another recent publication from us concerns the synthesis and isolation of a silaaldehyde and its functionalisation to other heavy carbonyl analogues . Addition of water to 1 a in the presence of GaCl 3 generated a white precipitate of the GaCl 3 /NHC‐stabilised heavy aldehyde analogue 10 in 61 % yield following recrystallisation (Scheme ).…”

Section: Discussionmentioning

confidence: 99%

“…Another recent publication from us concerns the synthesis and isolation of a silaaldehyde and its functionalisation to other heavy carbonyl analogues. [39] Addition of water to 1a in the presence of GaCl 3 generated a white precipitate of the GaCl 3 / NHC-stabilised heavy aldehyde analogue 10 in 61 % yield following recrystallisation (Scheme 11). Other Lewis acids such as boranes and ZnCl 2 gave mixtures of products, while the omission of a Lewis acid altogether gave a spirosiloxane (11) as the only isolated product, presumably by the decomposition of the intermediate Lewis acid-free silaaldehyde.…”

Section: Reactivity With Water and Gallium Chloridementioning

confidence: 99%

NHC‐Stabilised Silyliumylidene Ions

Powley

Inoue

2019

The Chemical Record

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Donor‐stabilised silyliumylidene ions, from the parent [R−Si:]+, are a class of low‐valent silicon species which have received increasing research interest in the last several years. This interest began in the fundamental synthesis and characterisation of these compounds, but has since started to include more investigation into their further reactivity after several stable NHC‐stabilised silyliumylidene ions were reported. This personal account briefly discusses the history of the still‐young field of silyliumylidene ions followed by a more detailed discussion of published work from our group on the further development of silyliumylidene chemistry over the last four years.

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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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The Quest for Stable Silaaldehydes: Synthesis and Reactivity of a Masked Silacarbonyl

Cited by 37 publications

References 56 publications

An Isolable Bis(Silanone–Borane) Adduct

An Isolable Bis(Silanone–Borane) Adduct

NHC‐Stabilised Silyliumylidene Ions

Low Valent Main Group Compounds in Small Molecule Activation

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