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  • 1
    Electronic Resource
    Electronic Resource
    Head-to-Head versus Head-to-Tail Dimerizations of Transient Silenes - The Solvent-Dependent Regiospecifity of the Dimerization of 2-(2-Methoxyphenyl)-1,1-bis(trimethylsilyl)silene (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1667-1672 
    Details
    ISSN: 1434-1948
    Keywords: Silicon ; Silenes ; 1,2-Disilacyclobutanes ; 1,3-Disilacyclobutanes ; Eliminations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The regiospecifity of the dimerization of the transient 2-(2-methoxyphenyl)-1,1-bis(trimethylsilyl)silene (6), synthesized by base-initiated trimethylsilanolate elimination from (2-methoxyphenyl)[tris(trimethylsilyl)silyl]methanol (5) according to a modified Peterson mechanism, decisively depends on the donating ability of the solvent in which the silene is generated. In ether, 6 undergoes a formal [2 + 2] dimerization to afford 3,4-bis(2-methoxyphenyl)-1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclobutane (12), whereas in toluene the head-to-tail [2 + 2] cyclodimer, 2,4-bis(2-methoxyphenyl)-1,1,3,3-tetrakis(trimethylsilyl)-1,3-disilacyclobutane (13) was obtained. 1,1-Bis(trimethylsilyl)-2-(2,4,6-trimethoxyphenyl)silene (18), similarly made by a modified Peterson reaction, under the same conditions reacted with the eliminated trimethylsilanolate with readdition at the polar Si=C bond to give, after hydrolysis, 2-(2,4,6-trimethoxybenzyl)-1,1,1,3,3,3-hexamethyl-2-(trimethylsiloxy)trisilane (19). A possible mechanism explaining the solvent-dependent regiospecificity of the dimerization of 6 is discussed. The structures of 12 and 13 were determined on the basis of NMR and MS data as well as X-ray structural analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Synthesis of Transient Silenes by a Modified Peterson Reaction (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 143-149 
    Details
    ISSN: 0009-2940
    Keywords: Silenes ; Silene dimerization ; 1,2-Disilacyclobutanes ; 2,3-Disilanaphthalene, tetrahydro- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(trimethylsilyl)silylmagnesium bromide, obtained in situ from tris(trimethylsilyl)silyllithium and magnesium bromide, reacts with acetone, pivalaldehyde, or 2,4,6-trimethylbenzaldehyde to give the (1-hydroxyalkyl)tris(trimethylsilyl)silanes (Me3Si)3SiC(OH)Me2 (1a), (Me3Si)3CH(OH)tBu (1b), and (Me3Si)3SiC(OH)Mes (1c), resp. After deprotonation with methyllithium in ether at -78°C 1a-c eliminate trimethylsilanolate according to a modified Peterson mechanism to form transient silenes (Me3Si)2Si=CR1R2 (6a: R1 = R2 = Me; 6b: R1 = H, R2 = tBu; 6c: R1 = H, R2 = Mes). In the absence of trapping agents these silenes dimerize, 6a leading to the linear dimer 1-isopropenyl-2-isopropyl-1,1,2,2-tetrakis(trimethylsilyl)disilane (7) and 6b giving the head-to-head cyclodimerization product (E)-3,4-di-tert-butyl-1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclobutane (8), whereas 6c in a very unusual cyclodimerization step affords (E)-1,2,3,8a-tetrahydro-1-mesityl-5,7,8a-trimethyl-2,2,3,3-tetrakis(trimethylsilyl)-2,3-disilanaphthalene (9). Compound 9 is the result of an unexpected [2 + 4] reaction, in which the silene formally acts as the monoene and - involving the aromatic substituent - simultaneously also as the diene. The reaction of 1a-c with methyllithium in THF at low temperature initiates 1,3-Si,O-trimethylsilyl migrations leading to (trimethylsiloxy)-[bis(trimethylsilyl)silyl]alkanes (Me3Si)2SiH-CR1R2OSiMe3 3a-c. Reaction of 1a-c with an excess of methyllithium, tert-butyllithium, or phenyllithium, leads to trisilanes (Me3Si)2-SiR3-CHR1R2 11a-e, formed by the addition of the organolithium reagent to the Si=C bond of the transient silences 6a-c. Deprotonation of 1b and 1c in the presence of 2,3-dimethyl-1,3-butadiene gives the [2 + 4] cycloadducts 6-tert-butyl-3,4-dimethyl-1,1-bis(trimethylsilyl)-1-sila-3-cyclohexene (12a) and 6-mesityl-3,4-dimethyl-1,1-bis(trimethylsilyl)-l-sila-3-cyclohexene (12b). For 8 and 9 the results of the X-ray analyses are given.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280210
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  • 3
    Electronic Resource
    Electronic Resource
    Controlled Conversion of the Transient 2-Mesityl-1,1-bis(trimethylsilyl)silene into a Tetrahydro-2,3-disilanaphthalene, a 1,2-Disilacyclobutane, or a 1,3-Disilacyclobutane (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1083-1088 
    Details
    ISSN: 0009-2940
    Keywords: Silenes ; Silene dimerization ; 1,2-Disilacyclobutanes ; 1,3-Disilacyclobutanes ; 2,3-Disilanaphthalene, tetrahydro- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mesityl[tris(trimethylsilyl)silyl]methanol (1) reacts with strong bases with elimination of trimethylsilanolate according to a Peterson-type mechanism, the outcome of the reaction being dependent on solvent, temperature, and nature of the organometallic base applied. Thus, 1 was converted by treatment with MeLi in ether at -78°C to (E)-1,2,3,8a-tetra -hydro-1-mesityl-5,7,8a-trimethyl-2,2,3,3-tetrakis (trimethylsi-lyl)-2,3-disilanaphthalene (3), formally a [2 + 4] cyclodimer of the transient silene (Me3Si)2Si=CHMes (2). The reaction of 1 with PhMgBr in THF after some days resulted in the formation of (Z)-3,4-dimesityl-1,1,2,2-tetrakis(trimethylsilyl) -1,2-disilacyclobutane (6) as the main product besides small quantities of 3, the polysilane (Me3SiSi(SiMe3)2CH2Mes (10), and the alkoxysilane (Me3Si)3SiCH(Mes)OSi(Si-Me3)2CH2Mes (7). Compound 6, the formal [2 + 2] cycloadduct of 2, can also be obtained by thermal treatment of 3 and is considered to be the thermodynamically more stable silene dimer whereas 3 is the kinetically preferred product. At high LiBr concentrations in the reaction mixture 1 was converted by PhMgBr in THF to (E)-2,4-dimesityl-1,1,3,3-tetrakis(tri- methylsilyl)-1,3-disilacyclobutane (13) besides 6 and [bis(tri-methylsilyl)silyl]mesityl(trimethylsiloxy)methane (11). The unforeseen formation of 13 is discussed as proceeding via the silene-lithium bromide adduct (Me3Si)2Si(Br)CH(Li)Mes (12). In the absence of LiBr 1 was converted by MeLi in THF at -78°C to 11 and the trisilane (Me3Si)2Si(Me)CH2Mes (4b). Probable pathways of the formation of all new compounds are discussed. For 6 and 13 the results of the X-ray structural analyses are given.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281105
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  • 4
    Electronic Resource
    Electronic Resource
    2-(2,4-Di-tert-butylphenyl)-1,1-bis(trimethylsilyl)silene and 2-(2,4,6-Tri-tert-butylphenyl)-1,1-bis(trimethylsilyl)silene - Two New Sterically Protected but Still Unstable Silaethenes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 15-20 
    Details
    ISSN: 0009-2940
    Keywords: Silenes ; Silene dimerization ; 1,2-Disilacyclobutanes ; 2,3-Disilanaphthalene, tetrahydro- ; 2-Silanaphthalene, tetrahydro- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (2,4-Di-tert-butylphenyl)tris(trimethylsilyl)silylmethanol (1a), prepared by the reaction of tris(trimethylsilyl)silylmagnesium bromide with 2,4-di-tert-butylbenzaldehyde, was deproto-nated by treatment with methyllithium in ether at -78°C to give the transient 2-(2,4-di-tert-butylphenyl)-1,1-bis(trimeth-ylsilyl)silene (3a), which dimerizes in a head-to-head fashion with the formation of (E)-/(Z)-3,4-bis(2,4-di-tert-butylphenyl)-1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclobutane (5). Besides 5 an unstable compound 4 was obtained, which was preliminarly assigned as 5,7-di-tert-butyl-1-(2,4-di-tert-bu-tylphenyl) -1,2,3,8a-tetrahydro-2,2,3,3-tetrakis(trimeth-ylsilyl)-1,2-disilanaphthalene (4), the formal [2 + 4] cyclodimer of 3a. Compound 4 gradually decomposes to give (E)-/(Z)-5, and is considered to be the kinetically preferred dimer of 3a, which is converted into the thermodynamically stable 5. 2,4,6-Tri-tert-butylbenzaldehyde reacts with tris(tri-methylsilyl)silyllithium resulting in the formation of 6,8-di-tert-butyl-1,2,3,4-tetrahydro-4,4-dimethyl-2,2- bis(trimethylsilyl)-2-silanaphthalene (6). Compound 6 is the product of the insertion of the Si=C bond into the C-H bond of an o-tert-butyl group of the intermediate 2-(2,4,6-tri-tert-butylphenyl)-1,1-bis(trimethylsilyl)silene (3b), which despite extreme steric shielding proved to be still unstable. For compounds (Z)-5 and 6 the results of the X-ray analyses are given.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290105
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