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The reactivity of bis(siloxy)silanone groups (Si-0)2Si=O stabilized on a silica surface with respect to H2 molecules was studied. The reaction was found to give the (Si-O)2SiH(OH) groups. The rate constant for this process was determined. Its activation energy in the 300–580 K temperature range is 13.4±0.3 kcal mol–1, and the enthalpy is 54±5 kcal mol–1. The activation energy for the reverse reaction,viz., elimination of a hydrogen molecule, is equal to 65 kcal mol–1. Quantum-chemical calculations of hydrogenation of F2Si=O and (HO)2Si=O, which are the simplest molecular models of the silanone groups, were performed. Data on the geometrical and electronic structures of transition states and on the effects of substituents at the silicon atom on the reactivity of the silanone groups in this process were obtained. The optical absorption band of the surface silanone groups was quantitatively characterized. Its maximum is located at 5.65±0.1 eV; the extinction coefficient at the maximum (220 nm) is (3±0.5) · 10–18 cm2 molec.–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1951–1958, August, 1996. 相似文献
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《Angewandte Chemie (International ed. in English)》2017,56(13):3699-3702
The first single‐component N‐heterocyclic silylene borane 1 (LSi‐R‐BMes2; L=PhC(Nt Bu)2; R=1,12‐xanthendiyl spacer; Mes=2,4,6‐Me3C6H2), acting as a frustrated Lewis pair (FLP) in small‐molecule activation, can be synthesized in 65 % yields. Its HOMO is largely localized at the silicon(II) atom and the LUMO has mainly boron 2p character. In small‐molecule activation 1 allows access to the intramolecular silanone–borane 3 featuring a Si=O→B interaction through reaction with O2, N2O, or CO2, and formation of silanethione borane 4 from reaction with S8. The SiII center in 1 undergoes immediate hydrogenation if exposed to H2 at 1 atm pressure in benzene, affording the silane borane 5‐H2 , L(H2)Si‐R‐BMes2. Remarkably, no H2 activation occurs if the single silylene LSiPh and Mes3B intermolecularly separated are exposed to dihydrogen. Unexpectedly, the pre‐organized Si–B separation in 1 enables a metal‐free dehydrogenation of H2O to give the silanone–borane 3 as reactive intermediate. 相似文献
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Dr. Shintaro Ishida Dr. Takashi Abe Dr. Fumiya Hirakawa Tomoyuki Kosai Katsuhiro Sato Prof. Dr. Mitsuo Kira Prof. Dr. Takeaki Iwamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15100-15103
A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at ?80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In 29Si NMR spectrum in [D8]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a [2+3] cycloadduct, respectively. The silanone remains intact in [D8]toluene below ?80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3‐silyl migration at higher temperatures. 相似文献
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Shintaro Takahashi Kazuki Nakaya María Frutos Antoine Baceiredo Nathalie Saffon‐Merceron Stphane Massou Norio Nakata Daisuke Hashizume Vicen Branchadell Tsuyoshi Kato 《Angewandte Chemie (International ed. in English)》2020,59(37):15937-15941
A novel N‐hetero‐RhI‐metallacyclic silanone 2 has been synthesized. The silanone 2 , showing an extremely large dimerization energy (ΔG=+86.2 kcal mol?1), displays considerable stability and persists in solution up to 60 °C. Above 120 °C, an intramolecular Csp3?H insertion occurs slowly over a period of two weeks leading to the bicyclic silanol 5 . The exceptional stability of 2 , related to the unusual electronic and steric effects of RhI‐substituent, should allow for a more profound study and understanding of these new species. Furthermore, the metallacyclic silanone 2 presents two reactive centers (Si=O and Rh), which can be involved depending upon the nature of reagents. Of particular interest, the reaction with H2 starts with the hydrogenation of RhI center leading to the corresponding RhIII‐dihydride complex 7 and it undergoes a cis/trans‐isomerization via a particular mechanism, demonstrating that addition‐elimination processes can also happen for silanones just like for their carbon analogues! 相似文献
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Cover Picture: Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol (Chem. Eur. J. 43/2015)
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Donor/Acceptor‐Stabilized 1‐Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction
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Dr. Morelia Lopez Reyes Dr. Thibault Troadec Dr. Ricardo Rodriguez Dr. Antoine Baceiredo Dr. Nathalie Saffon‐Merceron Prof. Vicenç Branchadell Dr. Tsuyoshi Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10247-10253
The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1‐silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1‐silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila‐β‐lactam 3 . Of particular interest, in the presence of 4‐dimethylaminopyridine (DMAP), 1‐silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1‐silaketene complex 8 and cis‐stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four‐membered‐ring intermediate, similar to that proposed by Chauvin and co‐workers for the transition‐metal‐based olefin metathesis. 相似文献
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Shintaro Takahashi Kazuki Nakaya Dr. María Frutos Dr. Antoine Baceiredo Dr. Nathalie Saffon-Merceron Dr. Stéphane Massou Dr. Norio Nakata Dr. Daisuke Hashizume Prof. Vicenç Branchadell Dr. Tsuyoshi Kato 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16071-16075
A novel N-hetero-RhI-metallacyclic silanone 2 has been synthesized. The silanone 2 , showing an extremely large dimerization energy (ΔG=+86.2 kcal mol−1), displays considerable stability and persists in solution up to 60 °C. Above 120 °C, an intramolecular Csp3−H insertion occurs slowly over a period of two weeks leading to the bicyclic silanol 5 . The exceptional stability of 2 , related to the unusual electronic and steric effects of RhI-substituent, should allow for a more profound study and understanding of these new species. Furthermore, the metallacyclic silanone 2 presents two reactive centers (Si=O and Rh), which can be involved depending upon the nature of reagents. Of particular interest, the reaction with H2 starts with the hydrogenation of RhI center leading to the corresponding RhIII-dihydride complex 7 and it undergoes a cis/trans-isomerization via a particular mechanism, demonstrating that addition-elimination processes can also happen for silanones just like for their carbon analogues! 相似文献
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