Carbon-13 and silicon-29 chemical shifts and coupling constants involving tris(trimethylsilyl)silyl systems

Brook, A. G.; Abdesaken, Fereydon; Gutekunst, G.; Plavac, Nicholas

doi:10.1021/om00067a018

Cited by 65 publications

(44 citation statements)

References 1 publication

(1 reference statement)

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“…[5] The 1 J SiÀC value of 1 is also almost the same as the 84 Hz reported for (Me 3 Si) 2 SiC(Ad)OSiMe 3 (Ad 1-adamantyl), [13] with a SiÀC bond length of 1.764 . [14] These results indicate the delocalized character of 1, which is supported by the calculated structure of a model compound 2.…”

Section: Synthesis and Properties Of An Overcrowdedsupporting

confidence: 68%

Synthesis and Properties of an Overcrowded Silabenzene Stable at Ambient Temperature

Wakita

Tokitoh²,

Okazaki³

et al. 2000

Angewandte Chemie Intl Edit

153

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Section: Synthesis and Properties Of An Overcrowdedsupporting

confidence: 68%

Synthesis and Properties of an Overcrowded Silabenzene Stable at Ambient Temperature

Wakita

Tokitoh²,

Okazaki³

et al. 2000

Angewandte Chemie Intl Edit

153

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“…Consistent with this explanation is the remarkably low-field chemical shift found for the sp 2 hybridized C atom and the relatively high-field position found for the 298i absorption of the sp 2 hybridized Si atom (Brook, Abdesaken, Gutekunst & Plavac, 1982). The crystal structure is normal in other respects, all bond lengths and angles lying within accepted ranges.…”

Section: Si(l)supporting

confidence: 52%

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

Nyburg¹,

Brook²,

Abdesaken³

et al. 1985

Acta Crystallogr C

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“…[41] The small 1 J Si,C values are known to indicate long SiÀC bond lengths and/or the small s character of the SiÀC bond, both of which lead to weak SiÀC bonds. Therefore, these results strongly suggest that the SiÀC bonds of the SiCN units are considerably weak and their strength decreases in the order 5 c > 5 d > 5 e with increasing bulkiness of the substituents.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Properties of the First Stable Silylene–Isocyanide Complexes

Takeda

Kajiwara

Suzuki

et al. 2003

Chemistry A European J

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The first stable silylene-isocyanide complexes, [Tbt(Mes)SiCNAr] (5 c: Ar=Tip, 5 d: Ar=Tbt, 5 e: Ar=Mes*; Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes=mesityl, Tip=2,4,6-triisopropylphenyl, Mes*=2,4,6-tri-tert-butylphenyl) were successfully synthesized by the reaction of a kinetically stabilized disilene, [Tbt(Mes)Si=Si(Mes)Tbt] (1), with bulky isocyanides, ArNC (3c-e). The spectroscopic data of 5 c-e and theoretical calculations for a model molecule indicated that 5 c-e are not classical cumulative compounds but the first stable silylene-Lewis base complexes. The reactions of 5 c-e with triethylsilane and 1,3-dienes gave the corresponding silylene adducts, and they underwent isocyanide-exchange reactions in the presence of another isocyanide at room temperature. These results indicate dissociation of complexes 5 c-e to the corresponding silylene 2 and isocyanides 3 c-e under very mild conditions. The reaction of 5 c with methanol gave the MeOH adduct 16, [Tbt(Mes)SiHC(OMe)NTip], which has a hydrogen atom on the silicon atom. This regioselectivity can be explained in terms of the contribution of zwitterionic resonance structures D and E, which have an anion on the silicon atom. This result indicates that 5 c is not a classical cumulene having Si=C double bonds that should react with methanol to give adducts bearing a methoxyl group on the silicon atom. Although the reactions of 5 c-e with electrophilic reagents such as methanol, hydrogen chloride, and methyl iodide gave the formal silylene adducts, the studies on the reaction mechanism by trapping experiments and the observation of the intermediate suggested that the reaction mainly or partially proceeds by initial nucleophilic attack of the silicon atom, as is the case in the formation of 16 in the reaction of 5 c with methanol. It was revealed that 5 c-e show the nucleophilicity of the silicon atom, most likely resulting from the contribution of the zwitterionic resonance structures D and E.

show abstract

Carbon-13 and silicon-29 chemical shifts and coupling constants involving tris(trimethylsilyl)silyl systems

Cited by 65 publications

References 1 publication

Synthesis and Properties of an Overcrowded Silabenzene Stable at Ambient Temperature

Synthesis and Properties of an Overcrowded Silabenzene Stable at Ambient Temperature

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

Synthesis and Properties of the First Stable Silylene–Isocyanide Complexes

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