Structure of 2-(1-adamantyl)-2-trimethylsiloxy-1,1-bis(trimethylsily)-1-silaethylene

Nyburg, S. C.; Brook, A. G.; Abdesaken, F.; Gutekunst, G.; Wong‐Ng, W.

doi:10.1107/s0108270185008848

Cited by 15 publications

(8 citation statements)

References 5 publications

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“…Figure 3 shows the molecular structure of 3b as determined by single-crystal X-ray crystallography. The geometry of the central Si–C moiety closely resembles the one observed for Brook’s acyclic silene (Me 3 Si) 2 Si=C(OSiMe 3 )Ad ( 6 ) 3 , 12 with nearly identical Si=C bond lengths (1.767 vs 1.762 Å) and an essentially planar C(1) atom (∑αC(1) = 359.8°). As compared to 6 , Si(1) in 3b is slightly more pyramidalized by 2°, while the twist angle around the Si=C bond in 3b is significantly smaller, as shown by the torsion angles Si(6)–Si(1)–C(1)–C(10) and Si(2)–Si(1)–C(1)–O(1), likely as a result of the incorporation of Si(1) into the cyclohexasilane cycle.…”

supporting

confidence: 57%

Stable Silenolates and Brook-Type Silenes with Exocyclic Structures

et al. 2014

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The first silenolates with exocyclic structures [(Me3Si)2Si(Si2Me4)2SiC(R)O]−K+ (2a: R = 1-adamantyl; 2b: mesityl; 2c: o-tolyl) were synthesized by the reaction of the corresponding acylcyclohexasilanes 1a–c with KOtBu. NMR spectroscopy and single-crystal X-ray diffraction analysis suggest that the aryl-substituted silenolates 2b,c exhibit increased character of functionalized silenes as compared to the alkyl-substituted derivative 2a due to the different coordination of the K+ counterion to the SiC(R)O moiety. 2b,c, thus, reacted with ClSiiPr3 to give the exocyclic silenes (Me3Si)2Si(Si2Me4)2Si=C(OSiiPr3)R (3b: R = Mes; 3c: o-Tol), while 2a afforded the Si-silylated acylcyclohexasilane 1d. The thermally remarkably stable compound 3b, which is the first isolated silene with the sp2 silicon atom incorporated into a cyclopolysilane framework, could be fully characterized structurally and spectroscopically.

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confidence: 57%

Stable Silenolates and Brook-Type Silenes with Exocyclic Structures

et al. 2014

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“…The adducts obtained have been used as “instant silenes” in cases where the noncomplexed silene was not stable. In one of his contributions on the topic, Wiberg offered the following speculation: A prerequisite for adduct formation seems to be a polar SiX double bond, as neither Brook’s sila enol ether, , which has a largely nonpolar silicon−carbon double bond, nor West’s or Masamune’s (symmetrical) disilenes have been reported to form stable adducts.…”

Section: Introductionmentioning

confidence: 99%

Formation of Formal Disilene Fluoride Adducts

et al. 2008

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Reactions of trisilylated silylfluorides with potassium tert-butoxide were found to give disilylated fluorosilylenoids. The latter undergo a self-condensation reaction, leading to the formation of beta-fluorodisilanyl anions, which may also be considered as fluoride adducts of disilenes. The stereochemical outcome of this self-condensation depends on the bulkiness of the silyl substituents. Thus, mixtures of diastereomers are obtained in some cases. Reaction of a disilene adduct with magnesium bromide triggers metal fluoride elimination and formation of the respective tetrasilylated disilene. Attempts to exchange one silyl group of the starting material for a methyl, phenyl, or tert-butyl group led to a different course of reaction for the methyl and phenyl cases. The tert-butyl-substituted example gave the expected disilene adduct, but it was not the main product.

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“…It is recognized that bond lengths from crystal structures may vary significantly from true values, or from those derived from ab initio calculations: no attempt was made here to correct for the different kinds of data being considered. The crystal structure data for the Wiberg silene MezSi=C(SiMeS)Si-Me(Bu-t)J3] were fairly accurately reproduced, as were the data for the Brook silene (Me3Si)zSi= C(OSiMeJAd [2], although in the latter case one significant problem was encountered. Thus, the angle =C-O-SiMe, reported in the crystal structure was remarkably large, 134", and the angle 0-Cs,,z--C (of the adamantyl group) was remarkably small (1 12.2").…”

Section: Resultsmentioning

confidence: 65%

“…The parameter lists given below meet the object of duplicating simultaneously the structures of simple silenes, such as silene [l], dimethylsilene [ 11, and bis(sily1)silene [ 13, as well as the reported crystal structures of (Me3Si)2Si=CAd(OSiMe3) [2] (Ad = 1 -adamantyl) and Me2Si=C(SiMe3)SiMe ( B U -~)~ [3], and in addition disilenes such as disilene 141, tetraniethyldisilene [4], and the crystalline disilenes tetramesityldisilene [5], trans-l,2-dimesityl-1,2-di(t-butyl)disilene [S], and tetra(2,6-diethyl-pheny1)disilene [6].…”

mentioning

confidence: 99%