Silicon Analogues of Carboxylic Acids: Synthesis of Isolable Silanoic Acids by Donor–Acceptor Stabilization

Xiong, Yun; Yao, Shenglai; Drieß, Matthias

doi:10.1002/ange.201002970

Cited by 42 publications

(19 citation statements)

References 32 publications

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“…In almost all cases, such reactive species have been analyzed only in matrix system or gas phases, although Driesss group has recently reported the synthesis of a persistent silanoic acid stabilized by a donor/acceptor system (VII). [9] To our knowledge, this is the first example of a perfectly stable silanoic acid derivative in solution and in solid state.…”

Section: Methodsmentioning

confidence: 95%

“…[16] In the 29 Si NMR spectrum, the chemical shift of the silacarbonyl function in 4 appears as a doublet at d = À77.4 ppm ( 2 J SiP = 14.9 Hz) in the range of the reported silanoic acid derivative (À73.2 ppm). [9] The pentacoordinate phosphorus center exhibits a drastic upfield shift in the . Notably, there are very few reports concerning experimental [17] and theoretical [18] studies on silanoic acids to date.…”

Section: Methodsmentioning

confidence: 99%

“…[7] Although these techniques allowed the synthesis of other silacarbonyl derivatives, such as silanoic acid anhydride VI [8] and pyridinium salts of silanoic acid VII, [9] only a few types of silacarbonyl compounds are available to date.…”

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confidence: 99%

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A Base‐Stabilized Sila‐β‐Lactone and a Donor/Acceptor‐Stabilized Silanoic Acid

et al. 2013

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The carbonyl group I is ubiquitous and without doubt one of the most important functional groups in organic chemistry; it characterizes many compounds such as ketones, aldehydes, carboxylic acids, and many other related compounds. In marked contrast, the synthesis of the heavier silicon analogue II is still elusive owing to the weak and strongly polarized Si-O p bond, which accounts for a very strong tendency to give thermodynamically stable polysiloxanes.[1]M. Driess and co-workers reported that the silanone function can be efficiently stabilized using a donor/acceptor system III.[2-3] A base-stabilized silanon complex with a transition metal (type III) has also recently been reported.[4] M. Driess and co-workers also demonstrated that the stabilization of such species can be achieved by coordination of electron-donating ligands on the silicon center (type IV), which allowed the isolation of the first examples of a basesupported silaurea [5] and a silanoic silyl ester V.[6] We have also recently reported the synthesis of the first donorstabilized silacyclopropan-1-one of type IV.[7] Although these techniques allowed the synthesis of other silacarbonyl derivatives, such as silanoic acid anhydride VI [8] and pyridinium salts of silanoic acid VII, [9] only a few types of silacarbonyl compounds are available to date.[10] Here we present the synthesis of the first base-stabilized sila-b-lactone VIII and its unique reactivity with alcohols leading to the formation of a silanoic acid IX, more precisely, silicic acid monoethyl ester, which is a silicon analogue of monoethyl carbonate.It was known that silylenes react with dioxygen (O 2 ) to generate the corresponding transient silaester.[11] Similarly, the base-stabilized silacycloprop-1-ylidene 1 [12] readily reacts with one equivalent of dioxygen at 5 8C to give selectively the corresponding base-supported sila-b-lactone 2 (Scheme 1).The reaction proceeds regio-and diastereoselectively, which was indicated by the 31 P NMR spectrum showing only two signals for the b-lactone 2 in the same proportions as those for 1 (51.3 and 47.7 ppm; diastereomer ratio: 92:8). Derivative 2 is stable under inert conditions and was isolated as colorless crystals in 51 % yield. In the 29 Si NMR spectrum the signal corresponding to the silanone function appears as a doublet (d = À52.7 ppm, 2 J PSi = 11.2 Hz) at slightly lower field compared to 1 (d = À87.5 ppm), but in the range of base-stabilized silanones. [5,7] The two carbon atoms of the lactone ring were observed as two doublets at relatively low field (d = 80.1 ppm, 1 J CP = 85.8 Hz and d = 47.4 ppm, 2 J CP = 13.6 Hz). The 1 H NMR spectrum shows a doublet for the proton of the lactone ring with a large coupling constant (d = 4.51 ppm, 3 J PH = 20.4 Hz).The structure of 2 was unambiguously confirmed by X-ray diffraction analysis (Figure 1).[13] The structure reveals an essentially planar b-lactone four-membered ring (AE8 = 359.88) with an oxygen atom (O2) inserted between the silicon (Si1) and carbon (C1) atoms attached to the phospho...

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Section: Methodsmentioning

confidence: 95%

Section: Methodsmentioning

confidence: 99%

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A Base‐Stabilized Sila‐β‐Lactone and a Donor/Acceptor‐Stabilized Silanoic Acid

et al. 2013

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“…The syntheses of stable silicon compounds have been inspired almost exclusively by their relationship with organic congeners. Silicon analogues of alkenes, [11] alkynes, [12] allenes, [13] and other unsaturated organic compounds with a C=X (X = O or S) functional group [14,15] have been prepared. The molec-ular and electronic structures of unsaturated compounds of silicon are very different from those of the corresponding carbon compounds in which s/p hybridization models are valid.…”

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confidence: 99%

A Dimer of Silaisonitrile with Two‐Coordinate Silicon Atoms

et al. 2011

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A specialty of silicon: A stable dimeric silaisonitrile (ArNSi:)2 (see picture; Ar=2,6‐bis(2,4,6‐triisopropylphenyl)phenyl) was prepared by the reduction of dichlorosilaimine IPr⋅Cl2SiNAr with KC8. The dimer is the first base‐free disilylene with two‐coordinate silicon atoms; reaction with trimethylsilyl azide affords the first bis(silaimine) (ArNSiNSiMe3)2 with three‐coordinate silicon atoms.

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“…Si(=O)(OH)‐Einheiten aufweisen (29, 30). Letztere sind in Form der B(C6F5)3‐Komplexe zersetzungsstabil 1_33…”

Section: Grundlegende Molekülchemie: Silicium Bis Bleiunclassified

Anorganische Chemie 2010

Fischer¹,

Weigand²,

Wolf³

et al. 2011

Nachr Chem

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Molekülchemie der Hauptgruppenelemente: Trends wie die Stabilisierung ungewöhnlicher Bindungsumgebungen durch Carbene, die Darstellung persistenter Radikale, neuartige komplexchemische Wirtsysteme und Cluster als Liganden setzen sich fort. Koordinationschemie: Neuartige Metall‐Metall‐Bindungen erregten große Aufmerksamkeit; der Trend, metallorganische Gerüstverbindungen als Reaktionsraum oder Modellsystem zu nutzen, setzt sich fort. Bioanorganik: Die Aktivierung kleiner Moleküle wie H2 und CH4 durch Metalloenzyme hielt letztes Jahr einige Überraschungen parat.

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Silicon Analogues of Carboxylic Acids: Synthesis of Isolable Silanoic Acids by Donor–Acceptor Stabilization

Cited by 42 publications

References 32 publications

A Base‐Stabilized Sila‐β‐Lactone and a Donor/Acceptor‐Stabilized Silanoic Acid

A Base‐Stabilized Sila‐β‐Lactone and a Donor/Acceptor‐Stabilized Silanoic Acid

A Dimer of Silaisonitrile with Two‐Coordinate Silicon Atoms

Anorganische Chemie 2010

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