107-46-0Relevant academic research and scientific papers
Reactions of organosilicon-group V compounds with nitrosyl chloride
Byrne, Joseph E.,Russ, Charles R.
, p. 357 - 360 (1970)
The reactions of (CH3)3SiN(CH3)2, (CH3)3SiP(CH3)2, and (CH3)3SiAs(CH3)2 with NOCl have been studied. The products observed are, respectively: (CH3)3SiCl and (CH3)2NNO; (CH3)3SiOSi(CH3)3, N2O, NO, N2, (CH3)3SiCl, (CH3)2P(O)Cl, and a glassy solid; (CH3)3SiOSi(CH3)3, N2O, and (CH3)2AsCl.
Siloxane derivatives of 2-mercaptobenzothiazole
Zhilitskaya, Larisa V.,Yarosh, Nina O.,Shagun, Lyudmila G.,Dorofeev, Ivan A.,Larina, Lyudmila I.
, p. 352 - 354 (2017)
First organosilicon captax derivatives were obtained from 2-mercaptobenzothiazole and 1-(iodomethyl)-1,1,3,3,3-pentamethyl-or 1,3-bis(iodomethyl)-1,1,3,3-tetramethyldisiloxanes in the absence or in the presence of bases.
Reactivity of Cyclic Silenolates Revisited
Haas, Michael,Leypold, Mario,Schuh, Lukas,Fischer, Roland,Torvisco, Ana,Stueger, Harald
, p. 3765 - 3773 (2017)
The stable exocyclic silenolates 2a-c (2a, R = Mes; 2b, R = o-Tol; 2c, R = 1-Ad) were fully characterized by NMR and UV-vis spectroscopy. According to spectroscopic and structural features, 2a-c are best described as acyl silyl anions (tautomeric structure I) in solution. This behavior is also reflected by the reaction of 2a,c with MeI. Both alkylation reactions take place at the corresponding silicon atom and lead to the formation of the methylated structures 4a,b in nearly quantitative yields. Furthermore, the thermal stability of exocyclic silenolates 2a,c was investigated. In the case of 2a, a thermally induced intramolecular sila-Peterson alkenation was observed at 60 °C. This transformation allowed straightforward access to 2-oxahexasilabicyclo[3.2.1]octan-8-ide 5 as a structurally complex, bicyclic silicon framework. In contrast to that, heating of 2c, as an example of an alkyl-substituted silenolate, led to an unexpected degradation to uncharacterized polymers. However, we were able to isolate the 1-adamantyl-substituted, bicyclic compound 8, which is structurally closely related to 5, by the treatment of 1,4-dipotassium-1,4-bis(trimethylsilyl)cyclohexasilane with 1 equiv of 1-adamantoyl chloride. Again an intramolecular sila-Peterson alkenation is responsible for the formation of 8. The mechanism for this highly selective reaction sequence is outlined and supported by density functional theory (DFT) calculations, which highlight the thermodynamic driving force and the low activation barriers of this multistep transformation.
Ether-like Si-Ge hydrides for applications in synthesis of nanostructured semiconductors and dielectrics
Tice, Jesse B.,Weng, Change,Tolle, John,D'Costa, Vijay R.,Singh, Rachna,Menendez, Jose,Kouvetakis, John,Chizmeshya, Andrew V. G.
, p. 6773 - 6782 (2009)
Hydrolysis reactions of silyl-germyl triflates are used to produce ether-like Si-Ge hydride compounds including H3SiOSiH3 and the previously unknown O(SiH2GeH3)2. The structural, energetic and vibrati
Mechanistic insights on azide-nitrile cycloadditions: On the dialkyltin oxide-trimethylsilyl azide route and a new vilsmeier-haack-type organocatalyst
Cantillo, David,Gutmann, Bernhard,Kappe, C. Oliver
, p. 4465 - 4475 (2011)
The mechanism of the azide-nitrile cycloaddition mediated by the known dialkylltin oxide-trimethylsilyl azide catalyst system has been addressed through DFT calculations. The catalytic cycle for this tin/silicon complex-based mechanism has been thoroughly examined, disclosing the most plausible intermediates and the energetics involved in the rate enhancement. In addition, a new catalyst, 5-azido-1-methyl-3,4-dihydro-2H-pyrrolium azide, is presented for the formation of tetrazoles by cycloaddition of sodium azide with organic nitriles under neutral conditions. The efficiency of this organocatalyst, generated in situ from N-methyl-2-pyrrolidone (NMP), sodium azide, and trimethylsilyl chloride under reaction conditions, has been examined by preparation of a series of 5-substituted-1H-tetrazoles. The desired target structures were obtained in high yields within 15-25 min employing controlled microwave heating. An in depth computational analysis of the proposed catalytic cycle has also been addressed to understand the nature of the rate acceleration. The computed energy barriers have been compared to the dialkylltin oxide-trimethylsilyl azide metal-based catalyst system. Both the tin/silicon species and the new organocatalyst accelerate the azide-nitrile coupling by activating the nitrile substrate. As compared to the dialkylltin oxide-trimethylsilyl azide method, the organocatalytic system presented herein has the advantage of higher reactivity, in situ generation from inexpensive materials, and low toxicity.
Bonding studies on zinc, cadmium, and mercury alkyls and amides, Zn(CH2EMe3)2 (E = C or Si) and M2 (M = Zn, Cd, or Hg). Heats of hydrolysis, standard heats of formation, and Zn-C and M-N (M = Zn, Cd, or Hg) bond energy terms
Guemruekcueoglue, Ismail E.,Jeffery, John,Lappert, Michael F.,Pedley, J. Brian,Rai, Audesh K.
, p. 53 - 62 (1988)
Calorimetric measurements have been carried out on the heats of hydrolysis of the homoleptic zinc alkyls Zn(CH2EMe3)2 (E = C or Si) and bis(trimethylsilyl)amides M2 (M = Zn, Cd, or Hg) at 25 +/- 0.01 deg C in aqueous hydrochloric (1 M; for the
1,2-Migration of the trimethylsilyl group in free radicals
Harris, Joanna M.,MacInnes, Iain,Walton, John C.,Maillard, Bernard
, p. C25 - C28 (1991)
EPR spectroscopic observations and product studies showed that the trimethylsilyl group undergos 1,2-migration from carbon to nitrogen in aminyl radicals, Me3SiCH2NH -> CH2NHSiMe3, and from carbon to oxygen in alkoxyl radicals, Me3SiCH2O -> CH2OSiMe3.
Generation and Reactivity of a NiIII2(μ-1,2-peroxo) Complex
Zhao, Norman,Filatov, Alexander S.,Xie, Jiaze,Hill, Ethan A.,Rogachev, Andrey Yu.,Anderson, John S.
, p. 21634 - 21639 (2020)
High-valent transition metal-oxo, -peroxo, and -superoxo complexes are crucial intermediates in both biological and synthetic oxidation of organic substrates, water oxidation, and oxygen reduction. While high-valent oxygenated complexes of Mn, Fe, Co, and Cu are increasingly well-known, high-valent oxygenated Ni complexes are comparatively rarer. Herein we report the isolation of such an unusual high-valent species in a thermally unstable NiIII2(μ-1,2-peroxo) complex, which has been characterized using single-crystal X-ray diffraction and X-ray absorption, NMR, and UV-vis spectroscopies. Reactivity studies show that this complex is stable toward dissociation of oxygen but reacts with simple nucleophiles and electrophiles.
Laser-powered homogeneous pyrolysis of 1,1-dimethyl-1-silacyclobutane in the presence of some common monomers
Pola, Josef,Cukanova, Dana,Minarik, Milan,Lycka, Antonin,Tlaskal, Jaroslav
, p. 23 - 34 (1992)
Laser-induced homogeneous pyrolysis of 1,1-dimethyl-1-silacyclobutane yields 1,1,3,3-tetramethyl-1,3-disilacyclobutane and ethene as major products.In the presence of vinyl acetate, allyl methyl ether, acrolein, methyl vinyl ether, methyl acrylate or meth
Catalytic Metal-Free Deoxygenation of Nitrous Oxide with Disilanes
Anthore-Dalion, Lucile,Nicolas, Emmanuel,Cantat, Thibault
, p. 11563 - 11567 (2019)
Because of its high kinetic stability, conditions to reduce the greenhouse gas N2O are limited; therefore, a better understanding of N2O chemistry and N-O bond cleavage is required. In this work, N2O was deoxygenated under metal-free conditions. Using disilanes as reducing agents and a catalytic amount of fluoride anions or alkoxides allowed a mild reduction at ambient pressure and temperature. DFT calculations unveiled the mechanism, which shows a nucleophilic addition of a silyl anion to the central N atom of N2O and release of N2 from a pseudo-Brook rearrangement.
