The stable silylene Si[(NCH2But)2C6H4-1,2]: Reactions with Group 14 element halides

Gehrhus, Barbara; Hitchcock, Peter B.; Jansen, Helen

doi:10.1016/j.jorganchem.2005.10.027

Cited by 22 publications

(11 citation statements)

References 25 publications

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“…The formation of a complex with a N-heterocyclic carbene is the only well documented example for a Lewis acid like reactivity of silylene 2a [17]. The most important reaction mode for silylenes 1, 2a, 3a is oxidative addition to give tetracoordinated silicon(IV) compounds [18][19][20][21]. For these transformations concerted [19] as well as stepwise radical mechanisms [20][21][22] are suggested.…”

Section: Reactivitymentioning

confidence: 99%

“…The most important reaction mode for silylenes 1, 2a, 3a is oxidative addition to give tetracoordinated silicon(IV) compounds [18][19][20][21]. For these transformations concerted [19] as well as stepwise radical mechanisms [20][21][22] are suggested. We examined several reactions which are characteristic for silylenes to review the effect of the N-aryl substituent on the reactivity of NHSis 9.…”

Section: Reactivitymentioning

confidence: 99%

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Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes

Zark

Schäfer

Mitra³

et al. 2010

Journal of Organometallic Chemistry

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Section: Reactivitymentioning

confidence: 99%

Section: Reactivitymentioning

confidence: 99%

Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes

Zark

Schäfer

Mitra³

et al. 2010

Journal of Organometallic Chemistry

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“…45 Belzner et al have recently reported insertions of transient silylenes, which are generated by thermolysis of the corresponding cyclotrisilanes, into Si-Cl bonds, 46 and Si-Cl bond insertion reactions of stable diarylgermylene and diarylstannylene compounds with tetrachlorosilane and trichloro(methyl)silane have been reported by Lappert et al 47 More recently, Gehrhus et al have reported the reactions of diaminosilylene 7 with various halosilanes. 48 Stable silylene 1 reacts smoothly with various chlorosilanes giving the corresponding Si-Cl bond insertion products. The reactions of 1 with tetrachlorosilane and dichlorodimethylsilane in hexane at room temperature afford the corresponding chlorinated disilanes 25 and 26 in 72 and 65% yields, respectively (Eq.…”

Section: Reactions With Chlorosilanesmentioning

confidence: 99%

A Helmeted Dialkylsilylene

Kira¹,

Iwamoto²,

Ishida³

2007

Bulletin of the Chemical Society of Japan

102

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Structural characteristics, spectroscopic properties, and unique reactions of a helmeted dialkylsilylene, 2,2,5,5-tetrakis(trimethylsilyl)silacyclopentane-1,1-diyl, that was synthesized as the first isolable dialkylsilylene and its application to the synthesis of novel silicon unsaturated compounds are surveyed. The silylene was found to be the least electronically perturbed among known stable silylenes by 29 Si NMR and UV-vis spectroscopies. The silylene reacts not only with well-known trapping reagents for transient silylenes, such as alcohols, triethylsilane, and 2,3-dimethylbutadiene, but also with less reactive haloalkanes and halosilanes to give the corresponding adducts. One-electron reduction of the silylene using alkali metals affords the corresponding radical anion as a relatively persistent species at low temperatures in solution. Irradiation of the silylene using visible light generates a singlet excited state with a lifetime of 80.5 ns, which reacts with various aromatic compounds and alkenes to give the corresponding silepins and siliranes in a highly regio-and stereoselective manner. The silylene is utilized for the synthesis of unique silicon unsaturated compounds, such as Si=X doubly bonded compounds (X ¼ S, Se, Te, C=NR, etc.), a trisilaallene, a 1,3-disilagermaallene, and silylene transition-metal complexes.

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“…It is wellknown in the literature that the reaction of two-coordinate silylene [{HCN(tBu)} 2 Si] with SnCl 2 results in a disproportionation reaction forming [{HCN(tBu)} 2 Si] 3 SnCl and Sn. 60 Amidinato silicon(II) amide [PhC(NtBu) 2 N(TMS) 2 Si] with SnCl 2 gives a simple adduct formation [PhC(NtBu) 2 N-(TMS) 2 Si→SnCl 2 ]. 61 However, the reaction of 1 with SnCl 2 led to a metathesis product 7 in 64% yield (Scheme 3) along with some decomposition products (see Scheme S4 for the proposed mechanism).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Motivated by the results of the GeCl 2 reaction, we sought to synthesize a similar type of compound with tin. It is well-known in the literature that the reaction of two-coordinate silylene [{HCN( t Bu)} 2 Si] with SnCl 2 results in a disproportionation reaction forming [{HCN( t Bu)} 2 Si] 3 SnCl and Sn . Amidinato silicon(II) amide [PhC(N t Bu) 2 N(TMS) 2 Si] with SnCl 2 gives a simple adduct formation [PhC(N t Bu) 2 N(TMS) 2 Si→SnCl 2 ] .…”

Section: Resultsmentioning

confidence: 99%

Reactivity of (TMS)₂N(η¹-Cp)Si═Si(η¹-Cp)N(TMS)₂ toward the Halides of Groups 13–15

et al. 2021

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In this paper, we have demonstrated the unique reactivity of a previously reported disilene [(TMS)2N(η1-Me5C5)SiSi(η1-Me5C5)N(TMS)2] (1) with the halides of groups 13–15, which resulted in the formation of silicon–E (E = B, Al, Ge, P) bonds. Treatment of 1 with Lewis acidic BCl3 led to the formation of a cationic boron species [Cp*BSi(Cl)2N(TMS)2)][BCl3SiCl3] (2). In contrast, the reaction of 1 with BCy2Cl afforded an oxidative addition product [(TMS)2N(η1-Me5C5)Si(BCy2)(Cl)] (3) via the insertion of a Si(II) atom into the B–Cl bond. Extending the reaction with its higher congener led to classical Lewis acid-base adducts, (TMS)2N(η1-Me5C5)Si→AlCl3 (4) and (TMS)2N(η1-Me5C5)Si→AlBr3 (5), respectively. The reaction of GeCl2 with 1 proceeded in a completely different manner and resulted in a hybrid dendrimeric compound [HGe(Si(Cl)2N(TMS)2)3] (6), whereas, with SnCl2, it led to Cp*SnCl (7). Lastly, the reaction of Ph2PCl followed the same pattern like Cy2BCl and led to the formation of an oxidative addition product [(TMS)2N(η1-Me5C5)Si(PPh2)(Cl)] (9) with a Si–P bond.

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The stable silylene Si[(NCH2But)2C6H4-1,2]: Reactions with Group 14 element halides

Cited by 22 publications

References 25 publications

Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes

Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes

A Helmeted Dialkylsilylene

Reactivity of (TMS)₂N(η¹-Cp)Si═Si(η¹-Cp)N(TMS)₂ toward the Halides of Groups 13–15

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The stable silylene Si[(NCH2But)2C6H4-1,2]: Reactions with Group 14 element halides

Cited by 22 publications

References 25 publications

Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes

Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes

A Helmeted Dialkylsilylene

Reactivity of (TMS)2N(η1-Cp*)Si═Si(η1-Cp*)N(TMS)2 toward the Halides of Groups 13–15

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Reactivity of (TMS)₂N(η¹-Cp)Si═Si(η¹-Cp)N(TMS)₂ toward the Halides of Groups 13–15