Three Stable 1-Silapropadienes

Eichler, Barrett E.; Miracle, Gary E.; Powell, Douglas R.; West, Robert

doi:10.1515/mgmc.1999.22.3.147

Cited by 29 publications

(27 citation statements)

References 15 publications

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“…The R–Si–R plane is orthogonal to the plane of the NHC ring. Thus, compounds NHC t Bu →1(R) may be considered as 1‐silaallenes, which are experimentally known 17. The first stable 1‐silaallene that could be isolated was synthesized by West and co‐workers in 1993 18.…”

Section: Methodsmentioning

confidence: 99%

Silavinylidene Stabilized by an N‐Heterocyclic Carbene: A Theoretically Predicted Stable Molecule

Andrada

et al. 2014

Chemistry A European J

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Quantum chemical calculations show that the N-heterocyclic carbene (NHC)-stabilized silavinylidene, NHC(tBu)→C=SiR2 is a strongly bonded complex, which has a linear arrangement of the donor and acceptor moieties. The molecule is the energetically lowest lying isomer of the NHC-stabilized R2CSi isomers and it is stable towards dimerization when R is a bulky substituent. The silavinylidene complex is the only species of the silylidene homologues NHC(tBu)→E=E'R2 (E, E' = C-Pb) which possesses a linear arrangement. The unusual bonding situation is explained in terms of donor-acceptor interactions between NHC(tBu) as σ donor and C=SiR2 in the doubly excited singlet state 3a1⇒2b2 which leads to a significantly shorter C-SiR2 bond compared with free C=SiR2 .

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Section: Methodsmentioning

confidence: 99%

Silavinylidene Stabilized by an N‐Heterocyclic Carbene: A Theoretically Predicted Stable Molecule

Andrada

et al. 2014

Chemistry A European J

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“…Other stable silaallenes have been synthesized by a slightly different route involving an intermolecular addition of tert -butyllithium to a vinylfluorosilane. 10a,b, The reactivity of these silaallenes has been relatively poorly studied. With water and methanol, addition of the O−H bond to the SiC double bond was observed,17a and a [2 + 2] cycloaddition occurred with benzaldehyde 17a. Thermolysis,17a photolysis,17b and reactions with acids 17 resulted in a cyclization of the SiC double bond with the substituents on the silicon or on the terminal carbon atoms.…”

Section: Silaallenes and Germaallenes >E14cc< (E14 = Si Ge)mentioning

confidence: 99%

“…With water and methanol, addition of the O−H bond to the SiC double bond was observed,17a and a [2 + 2] cycloaddition occurred with benzaldehyde 17a. Thermolysis,17a photolysis,17b and reactions with acids 17 resulted in a cyclization of the SiC double bond with the substituents on the silicon or on the terminal carbon atoms. Silaallenes seem less reactive than silenes, since they are stable for days in the presence of oxygen and moisture at room temperature and react only after heating.…”

Section: Silaallenes and Germaallenes >E14cc< (E14 = Si Ge)mentioning

confidence: 99%

Group 14 and 15 Heteroallenes ECC and ECE‘

and

Ranaivonjatovo

2007

Organometallics

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This review describes the synthesis, physical properties, and some aspects of the reactivity of heteroallenes, namely the heavier congeners of allenes containing one or two doubly bonded heavier elements of groups 14 (Si, Ge, Sn) and 15 (P, As, Sb). The key factor for their preparation lies in the use of synthetic methods effective under mild conditions: i.e., in many cases, the dehalogenation at low temperature of dihaloheteropropenes by lithium derivatives. Their stabilization was successful, owing to very bulky substituents; substituted aromatic groups were often used, particularly the 2,4,6-tri-tert-butylphenyl group (supermesityl). Whereas various types of heteroallenes containing a doubly bonded element of the second or third long row have been isolated, their heavier counterparts of the fourth row have only been postulated as reaction intermediates.

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“…However, a potential limitation of this approach is the instability of terphenyl substituents against insertion reactions, as was found in the case of an unstable disilyne with this type of substituent . On the basis of the conjugate addition of organolithiums to alkynylhalosilanes, which with a proper choice of substituents yields silaallenes (as established by West), − we wanted to extend the scope of this reaction type to functional silaallenes. Earlier we tried to perform a conjugate addition of PhLi to a terphenyl-substituted alkynyl silane ( 1 ); however the nucleophile simply displaces the two halogen atoms at silicon .…”

Section: Introductionmentioning

confidence: 99%

Formation of a Silylated 1-Silaallene via an Intermediate 1-Chloro-1-silaallene

et al. 2010

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Twofold conjugate addition to a 2,6-dimesitylphenyl-substituted dihaloalkynylsilane yields a silylsubstituted 1-silaallene rather than the isomeric silyne. The dehalogenative intramolecular carbometalation elimination using t-BuLi proceeds via stepwise dehalogenation involving an intermediate 1-chloro-1silaallene. Our findings are backed by crystal structure analyses, spectroscopic data, and ab initio calculations. The completely dehalogenated 1-silaallene provides a silyl group at the silaallene core itself, which should allow further functionalization.

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Three Stable 1-Silapropadienes

Cited by 29 publications

References 15 publications

Silavinylidene Stabilized by an N‐Heterocyclic Carbene: A Theoretically Predicted Stable Molecule

Silavinylidene Stabilized by an N‐Heterocyclic Carbene: A Theoretically Predicted Stable Molecule

Group 14 and 15 Heteroallenes ECC and ECE‘

Formation of a Silylated 1-Silaallene via an Intermediate 1-Chloro-1-silaallene

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