Oxidation processes in the gas-phase silane-ozone system. Chemiluminescent emission and the molecular structure of H2SiO

Glinski, Robert J.; Gole, James L.; Dixon, David A.

doi:10.1021/ja00307a010

Cited by 59 publications

(28 citation statements)

References 3 publications

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“…Silicon–oxygen doubly bonded compounds (silanones) have been one of the most attractive species as silicon versions of carbonyl compounds from the beginning of the silicon chemistry 1. 2 In contrast to carbonyl compounds, silanones are highly reactive and therefore they were originally only evidenced as reactive intermediates that can be observed in argon matrix at low temperature3, 4 or were trapped during thermal decomposition of the corresponding precursors 5–7. Since the first pioneering works of donor and acceptor stabilized SiO species ( A ) by Driess et al 8.…”

Section: Methodsmentioning

confidence: 99%

Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol

Ishida

Abe

Hirakawa

et al. 2015

Chemistry A European J

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A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at -80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In (29) Si NMR spectrum in [D8 ]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a [2+3] cycloadduct, respectively. The silanone remains intact in [D8 ]toluene below -80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3-silyl migration at higher temperatures.

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Section: Methodsmentioning

confidence: 99%

Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol

Ishida

Abe

Hirakawa

et al. 2015

Chemistry A European J

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“…Evidence for their exis-not suitable for reactive molecules whose spectra are already tence in the gas phase was finally provided by chemilumines-difficult to observe in the ground state. However, using cercent emission (9) and mass spectrometry (10). tain approximations it is possible to estimate the structure of a molecule from the rotational constants of its isotopoThe study of H 2 SiO is also of technical interest since this molecule is predicted as a deposition precursor of silicon mers.…”

Section: Introductionmentioning

confidence: 99%

Experimentally Determined Structure of H2SiO by Rotational Spectroscopy and Isotopic Substitution

Bogey

Delcroix

Walters

et al. 1996

Journal of Molecular Spectroscopy

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“…Thanks to the exceptionally strong electron-donating phosphonium bora-ylide substituent, the lifetime at room temperature of the silanone is dramatically extended (t 1/2 = 4days) compared to the related (amino)(phosphoniumylide)silanone VI (t 1/2 = 5h), allowing easier manipulation and its use as precursor of new valuable silicon compounds.T he interaction of silanone with aweak Lewis acid such as MgBr 2 increases further its stability (no degradation after 3weeks at room temperature).Incontrast to carbonyl compounds (I), probably one of the most important functional group in organic chemistry,t he heavier silicon analogue,s ilanones (II), are generally highly reactive transient species [1] that were only observed either in argon matrix at low temperature [2] or in the gas phase [3] and were evidenced by trapping reactions. Thanks to the exceptionally strong electron-donating phosphonium bora-ylide substituent, the lifetime at room temperature of the silanone is dramatically extended (t 1/2 = 4days) compared to the related (amino)(phosphoniumylide)silanone VI (t 1/2 = 5h), allowing easier manipulation and its use as precursor of new valuable silicon compounds.T he interaction of silanone with aweak Lewis acid such as MgBr 2 increases further its stability (no degradation after 3weeks at room temperature).…”

mentioning

confidence: 99%

“…Incontrast to carbonyl compounds (I), probably one of the most important functional group in organic chemistry,t he heavier silicon analogue,s ilanones (II), are generally highly reactive transient species [1] that were only observed either in argon matrix at low temperature [2] or in the gas phase [3] and were evidenced by trapping reactions. [4] Silanones present as trongly polarized Si=Od ouble bond (Si d+ ÀO dÀ )w ith ac onsiderably large bond energy difference between SiO-p and SiO-s bonds, [5] and therefore,t hey easily oligomerize to give polysiloxanes.…”

mentioning

confidence: 99%

Cyclic (Amino)(Phosphonium Bora‐Ylide)Silanone: A Remarkable Room‐Temperature‐Persistent Silanone

et al. 2017

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As ilanone substituted by bulkya mino and phosphonium bora-ylide substituents has been isolated in crystalline form. Thanks to the exceptionally strong electron-donating phosphonium bora-ylide substituent, the lifetime at room temperature of the silanone is dramatically extended (t 1/2 = 4days) compared to the related (amino)(phosphoniumylide)silanone VI (t 1/2 = 5h), allowing easier manipulation and its use as precursor of new valuable silicon compounds.T he interaction of silanone with aweak Lewis acid such as MgBr 2 increases further its stability (no degradation after 3weeks at room temperature).Incontrast to carbonyl compounds (I), probably one of the most important functional group in organic chemistry,t he heavier silicon analogue,s ilanones (II), are generally highly reactive transient species [1] that were only observed either in argon matrix at low temperature [2] or in the gas phase [3] and were evidenced by trapping reactions. [4] Silanones present as trongly polarized Si=Od ouble bond (Si d+ ÀO dÀ )w ith ac onsiderably large bond energy difference between SiO-p and SiO-s bonds, [5] and therefore,t hey easily oligomerize to give polysiloxanes. [6] Recently,e asy-to-handle silanones stabilized as donor-acceptor or donor complexes,h ave been reported. [7][8][9][10][11] Nevertheless,t he synthesis of stable threecoordinate silanone derivatives remains ad ifficult task, although the heavier analogue germanone III,well kinetically stabilized by bulky aryl substituents,h as been isolated by Matsuo/Tamao et al. [12] At present only three examples are reported:1 )the transition-metal-substituted silanone IV, isolated at RT by Filippou et al., [13] 2) the cyclic dialkylsilanone V,c haracterized in situ at À80 8 8Cb yt he group of Iwamoto, [14] and 3) the relatively persistent (amino)-(ylide)silanones VI,r eported by us. [15] Therefore,t heir synthetic use is still limited because of the scarcity and limited lifetime (0.5-5 h, at RT for VI). Herein we report that the introduction of as trongly donating phosphonium boraylide substituent considerably extends the lifetime of silanone 2 (t 1/2 = 4days,a tR T), which allows easier manipulation to study its properties and reactivity.Recently,w eh ave described that the electropositive boron-based substituent (phosphonium bora-ylide), [16,17] with an exceptionally strong electron donating character,i s able to efficiently stabilize highly reactive species such as Nheterocyclic silylene 1,the related silylium ion and transitionmetal-silylene complexes featuring at rigonal-planar geometry around the silicon center. [18] We thus have considered the use of the same set of substituents for the stabilization of the silanone moiety.T aking into account the better donating ability of phosphonium bora-ylide function than that of classical (carbo)ylides, [18] we can expect abetter stabilization effect with this substituent set than that used for the previously persistent silanone VI.The( amino)(bora-ylide)silylene 1 [15] immediately reacts with N 2 Oi nT HF solution, at À20...

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Oxidation processes in the gas-phase silane-ozone system. Chemiluminescent emission and the molecular structure of H2SiO

Cited by 59 publications

References 3 publications

Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol

Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol

Experimentally Determined Structure of H2SiO by Rotational Spectroscopy and Isotopic Substitution

Cyclic (Amino)(Phosphonium Bora‐Ylide)Silanone: A Remarkable Room‐Temperature‐Persistent Silanone

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