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Silenes, reactions

A second category of silene reactions involves interactions with tt-bonded reagents which may include homonuclear species such as 1,3-dienes, alkynes, alkenes, and azo compounds as well as heteronuclear reagents such as carbonyl compounds, imines, and nitriles. Four modes of reaction have been observed nominal [2 + 2] cycloaddition (thermally forbidden on the basis of orbital symmetry considerations), [2 + 4] cycloadditions accompanied in some cases by the products of apparent ene reactions (both thermally allowed), and some cases of (allowed) 1,3-dipolar cycloadditions. [Pg.28]

The following examples in this section illustrate that the silylcarbene-to-silene rearrangement and subsequent silene reactions are common also under nonmatrix conditions. The early research on this topic was reviewed in 197937. [Pg.715]

The [47r(ketone)-27T (silene)] reaction mode is dominant for the alkyl substituted silenes 149 and 150 The initially formed product is 479, which isomerizes in the dark in a non-reversible reaction to the siloxetane 480 (equation 159)235. [Pg.961]

The focus of the section on silene reaction kinetics is mainly on studies of bimolecular reactions of transient silene derivatives, because little absolute kinetic data exist for the reactions of stable derivatives and there have been few quantitative studies of the kinetics of unimolecular isomerizations such as ,Z-isomerization and pericyclic rearrangements, although a number of examples of such reactions are of course well known. In contrast, most of the studies of disilene reaction kinetics that have been reported have employed kinetically stable derivatives, and E,Z-isomerization has thus been fairly well characterized. The paucity of absolute rate data for unimolecular isomerizations of transient silenes and disilenes is most likely due to the fact that it is comparatively difficult to obtain reliable data of this type for transient species whose bimolecular reactions (including dimerization) are so characteristically rapid, unless the unimolecular process is itself relatively facile. Such instances are rare, at least for transient silenes and disilenes at ambient temperatures. [Pg.950]

Over the past ten years, absolute rate data have been reported on the kinetics of several bimolecular silene reactions in solution, including both head-to-tail and head-to-head dimerization the [l,2]-addition reactions of nucleophilic reagents such as water, aliphatic alcohols, alkoxysilanes, carboxylic acids and amines and the ene-addition, [2 + 2]-cycloaddition and/or [4 + 2]-cycloaddition of ketones, aldehydes, esters, alkenes, dienes and oxygen. The normal outcomes of these reactions are summarized in Scheme 1. [Pg.954]

Several examples were discussed earlier of the use of substituent effects for the elucidation of the mechanisms of silene reactions with nucleophilic reagents. For example, the trends in the rate constants for reaction of the series of 1,1 -diarylsilenes 19a-e with alcohols, acetic acid, amines, methoxytrimethylsilane and acetone all indicate that inductive electron-withdrawing substituents at silicon enhance the reactivity of the Si=C bond, and are consistent with a common reaction mechanism in which reaction is initiated by the formation of an intermediate complex between the silene and the nucleophile. [Pg.994]

The effects of substituting a phenyl group for —H or —Me at the silicon end of the Si=C bond has different effects on the rates of silene reactions depending on the substituents present at carbon. For example, the l,3,5-(l-sila)hexatriene derivatives 21a-c exhibit a significant decrease in reactivity toward methanol and acetone with increasing phenyl substitution (Table 11). This too is consistent with the stepwise mechanisms proposed for... [Pg.994]

Silene Reactions with Organic Dienes. The second example of reactions wdll concern Diels-Alder reactions of silenes. Certainly, as was already mentioned, the diene additions to silaethenes occur much faster than those to ethenes. Over and above that, in most eases other reactions operate in addition. As is shown in Scheme 10, the [4+4] cycloaddition of silaetiienes with 2,3-dimethyl-l,3-butadiene (DMB) leads - independently of tiie direction of silaethene addition to DMB - to one and the same [4+2]... [Pg.378]

Silene Reaction barrier (kcal mol - ) Orbital energies (eV) Charge density ... [Pg.124]

Thus, the silene reaction with ketones represents a formal analogy of the Wittig olefin synthesis. Silanone is believed to be formed, since its trimer and other oligomers are isolated from the final product mixtures. Thermal reactions of the known stable 2-siloxetanes are quite complex, but at least in some cases the expected olefin is formed110,244. [Pg.1120]

Compound 59a underwent intermolecular reactions characteristic of silenes (Scheme 19). Water added instantly across the Si=C double bond of the I -silaallene is expected to give vinylhydroxysilane 65 in 71% yield, and methanol was added... [Pg.19]

Matrix IR spectra of various silenes are important analytical features and allow detection of these intermediates in very complex reaction mixtures. Thus, the vibrational frequencies of Me2Si=CH2 were used in the study of the pyrolysis mechanism of allyltrimethylsilane [120] (Mal tsev et al., 1983). It was found that two pathways occur simultaneously for this reaction (Scheme 6). On the one hand, thermal destruction of the silane [120] results in formation of propylene and silene [117] (retroene reaction) on the other hand, homolytic cleavage of the Si—C bond leads to the generation of free allyl and trimethylsilyl radicals. While both the silene [117] and allyl radical [115] were stabilized and detected in the argon matrix, the radical SiMc3 was unstable under the pyrolysis conditions and decomposed to form low-molecular products. [Pg.46]

UV photolysis (Chapman et al., 1976 Chedekel et al., 1976) and vacuum pyrolysis (Mal tsev et al., 1980) of trimethylsilyldiazomethane [122]. The silene formation occurred as a result of fast isomerization of the primary reaction product, excited singlet trimethylsilylcarbene [123] (the ground state of this carbene is triplet). When the gas-phase reaction mixture was diluted with inert gas (helium) singlet-triplet conversion took place due to intermolecular collisions and loss of excitation. As a result the final products [124] of formal dimerization of the triplet carbene [123] were obtained. [Pg.47]

Nowadays silenes are well-known intermediates. A number of studies have been carried out to obtain more complex molecules having Si=C double bonds. Thus, an attempt has been made to generate and stabilize in a matrix 1,1-dimethyl-l-silabuta-l,3-diene [125], which can be formed as a primary product of pyrolysis of diallyldimethylsilane [126] (Korolev et al., 1985). However, when thermolysis was carried out at 750-800°C the absorptions of only two stable molecules, propene and 1,1-dimethylsilacyclobut-2-ene [127], were observed in the matrix IR spectra of the reaction products. At temperatures above 800°C both silane [126] and silacyclobutene [127] gave low-molecular hydrocarbons, methane, acetylene, ethylene and methylacetylene. A comparison of relative intensities of the IR... [Pg.47]

Photolytic generation of silene Me3Si(Me)C=SiMe2 in the presence of an excess of D20 or a trace of H20 affords disiloxanes 25, presumably via condensation of the silanol 26 in the case of D20, or by reaction of the silanol 27 with further silene in the case of H20 (Scheme 7) (138, 139). [Pg.177]

Another variant of the above-mentioned routes to silenes involved treatment of the carbinols (Me3Si)3SiC(OH)RR, formed from the addition of organometallic reagents R Li to polysilylacylsilanes, with bases such as NaH64 or MeLi,57,64 leading to the formation of alkoxides. These alkoxides spontaneously lost trimethylsilanolate ion, yielding silenes references for these reactions are listed in Table I. [Pg.79]

Silenes from the Reaction of Silenes with RMgX... [Pg.82]


See other pages where Silenes, reactions is mentioned: [Pg.177]    [Pg.115]    [Pg.117]    [Pg.32]    [Pg.340]    [Pg.1008]    [Pg.177]    [Pg.115]    [Pg.117]    [Pg.32]    [Pg.340]    [Pg.1008]    [Pg.6]    [Pg.45]    [Pg.31]    [Pg.32]    [Pg.177]    [Pg.178]    [Pg.178]    [Pg.71]    [Pg.76]    [Pg.77]    [Pg.78]    [Pg.78]    [Pg.78]    [Pg.79]    [Pg.80]    [Pg.82]    [Pg.82]    [Pg.83]    [Pg.84]   
See also in sourсe #XX -- [ Pg.3 ]

See also in sourсe #XX -- [ Pg.26 ]




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Alcohols, reactions with silenes

Aldehydes, reactions with silenes

Alkenes reactions with silenes

Azides, reactions with silenes

Bimolecular reactions, silenes

Brook silenes reactions

Brook-type silenes reactions

Butadiene, reactions with silenes

Carbonyl compounds, reactions with silenes

Cycloaddition reactions silenes

Dienes, reactions with silenes

Imines, reactions with silenes

Isobutene, reactions with silene

Ketones reactions with silenes

Kinetics, silene reactions

Kinetics, silene reactions dimerization

Kinetics, silene reactions formation

Oxygen, reaction with silenes

Propenal, reaction with silenes

Propene, reaction with silene

Reactions of Silenes Additions to the Double Bond

Rearrangement reactions silenes

Rearrangement reactions silylene-silene

Silene, elimination-addition reaction

Silene-Type Species in Elimination-Addition Reactions

Silenes

Silenes 2+4]cycloaddition reactions with diene

Silenes Peterson reaction

Silenes addition reactions

Silenes chemical reactions

Silenes via retro Diels-Alder reaction

Wiberg silenes, reactions

Wiberg silenes, reactions with dienes

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