Reactions of Triethylsilane and Diethylsilane with Inorganic Halides and Acids

Anderson, Herbert H.

doi:10.1021/ja01552a022

Cited by 39 publications

(29 citation statements)

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“…Potassium permanganate [1], hydrogen peroxide on a Zeolite catalyst [2], and perbenzoic acid [3] convert trialkyl(aryl)silanes to corresponding hydroxy derivatives. Triethylsilane and triethylgermane react with mineral acids (H 2 SO 4 , HNO 3 ), as well as with Ag 2 O at the boiling points of the hydrides to form siloxane and germanoxane [4].Over the past years dimethyldioxirane [5, 6] has been offered as a mild oxidant that converts trialkylsilanes of various structure to hydroxysilanes. The reaction involves the Si3H bond and occurs at temperatures ranging from 370oC to 20oC with a high conversion and selectivity by the molecular and radical mechanisms, the first prevailing.…”

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“…and Ph 3 Ge . radicals in the reaction of the corresponding hydrides with Al(OBu-t) 3 3hydroperoxide III in benzene at 20oC by means of ESR in the form of spin adducts 1 and 2 with 2,6-di-tert-butyl-p-benzoquinone [29] [scheme (4)]. …”

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“…Evidence for this scheme was provided by the isolation of hydroxytriphenylsilane in the oxidation of Ph 3 SiH with the Ph 3 GeOOH3Ti(OBu-t) 4 system. The fact that the peroxide bond in the metalcontaining peroxide can be oxidized with element hydrides was confirmed by the reactions of a fairly stable peroxide (t-BuO) 2 AlOOBu-t [22] with Et 3 GeH, as well as with triethyl-and triphenylsilanes (C 6 H 6 , room temperature).…”

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“…Special experiments were performed to establish that the dehydrating agent for hydroxytriphenylgermane can be alcoholate II. Hence, mixing of benzene solutions of Ti(OBu-t) 4 and Ph 3 GeH (molar ratio 1 : 1, 20oC) resulted in precipitation of about 0.5 mol of hexaphenylgermanoxane within 5310 min. Therewith, about 0.1 mol of t-BuOOH was liberated.…”

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Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

et al. 2005

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Trialkyl(aryl)silanes and -germanes effectively react with metal (Al, Ti) tert-butylate3tert-butylhydroperoxide under mild conditions (room temperature, benzene or tetrachloromethane) mainly by the element3hydrogen bond. The character of the products depends on the nature of the element, the structure of the radical bound to it, and the solvent. The process is radical in nature. It includes the stages of formation of element-centered radicals and their reaction with the oxygen generated by the system. The intermediate organometallic peroxides can also acts as oxidants for the element (Si, Ge)3hydrogen bonds.The oxidative activity of organosilicon and organogermanium hydrides depends on the structure of the radicals bound with the heteroatom and the nature of the oxidant. Potassium permanganate [1], hydrogen peroxide on a Zeolite catalyst [2], and perbenzoic acid [3] convert trialkyl(aryl)silanes to corresponding hydroxy derivatives. Triethylsilane and triethylgermane react with mineral acids (H 2 SO 4 , HNO 3 ), as well as with Ag 2 O at the boiling points of the hydrides to form siloxane and germanoxane [4].Over the past years dimethyldioxirane [5, 6] has been offered as a mild oxidant that converts trialkylsilanes of various structure to hydroxysilanes. The reaction involves the Si3H bond and occurs at temperatures ranging from 370oC to 20oC with a high conversion and selectivity by the molecular and radical mechanisms, the first prevailing.The reaction of organosilicon hydrides with ozone at 370oC to 380oC involves formation of hydrotrioxides R 3 SiOOOH [639]. At elevated temperatures, the latter decompose with liberation of singlet oxygen, hydroxysilane, and, to a smaller degree, siloxane [6,8]. The mechanism of the decomposition of silicon hydrotrioxides is mostly molecular.Silicon and germanium monohydrides are sufficiently stable toward free oxygen. Triphenylsilane undergoes oxidation to Ph 3 SiOH, initiated by benzoyl peroxide (C 6 H 6 , 95oC) [10]. However, the ability of R 3 GeH to oxidation is much dependent on the structure of the radical. Triphenylgermane is extremely slowly oxidized by atmospheric oxygen [11,12], but tricyclohexylgermane is fast oxidized on exposure to air to form tricyclohexylgermanol.Hence, E3H can bonds can be oxidized with a fairly broad range of reagents, and the reactions are accelerated by radical initiators. There is no information in the literature concerning reactions of silicon and germanium hydrides with oxidative systems comprising organoelement compounds or element alcoholates and hydroperoxides, that are known as effective and selective oxidants for C3H bonds in various substrates [13].It was previously shown that aluminum and titanium tert-butylates (I and II) react with tert-butylhydroperoxide (III) at a 1 : 2 ratio under mild conditions (C 6 H 6 , CCl 4 , 20oC) via formation of metalcontaining trioxides [14,15]. The latter decompose with evolution of oxygen, including singlet oxygen, as well as homolytically by the peroxide bonds with generation of alkoxyl and pero...

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Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

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Ionic and Organometallic‐Catalyzed Organosilane Reductions

Larson

Fry²

2008

Organic Reactions

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This chapter presents a critical review of synthetically useful variations of ionic methods for hydrogenation of organic compounds. In practice ionic hydrogenation involves the formal introduction of hydride from a donor source to an electron‐deficient carbon center. In this chapter, organosilicon hydrides are used as the source of ionic hydride with the goal of completing and updating earlier review work. Organosilicon compounds with at least one Si‐H bond have the ability to serve as mild‐air and water‐stable sources of hydrides and, thus, have reducing properties. In general, organosilicon hydrides do not undergo spontaneous reactions with organic compounds unless the organic substrate is a reasonably strong electrophile or the silane is first activated by the interaction of a nucleophilic species with a nucleophilic center. The organosilicon hydrides are covalent compounds that have little or no nucleophilic properties on their own. The use of these hydrides often provides a means of effecting reductions of organic substrates under very mild conditions and with excellent functional group selectivity. Consideration of the nature of the Si‐H bonds provides insight into the chemical behavior of these hydrides. Enhanced hydridic nature manifests itself in the chemical behavior of hydrosilanes.

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In Reductions of Metal Oxides

Towl¹

1986

Inorganic Reactions and Methods

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Reactions of Triethylsilane and Diethylsilane with Inorganic Halides and Acids

Cited by 39 publications

References 8 publications

Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

Ionic and Organometallic‐Catalyzed Organosilane Reductions

In Reductions of Metal Oxides

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