1118-02-1Relevant articles and documents
Cyanogen formation during asymmetric cyanohydrin synthesis
Chechik, Victor,Conte, Marco,Dransfield, Trevor,North, Michael,Omedes-Pujol, Marta
, p. 3372 - 3374 (2010)
During asymmetric cyanohydrin synthesis catalysed by vanadium Voxo(salen) complexes, the catalysts are reduced to vanadium IVoxo(salen) as determined by EPR spectroscopy; the reducing agent is cyanide which is oxidised to cyanogen via a non-radical mechanism.
Photochemical synthesis of a stable terminal uranium(VI) nitride
Barluzzi, Luciano,Scopelliti, Rosario,Mazzanti, Marinella
, p. 19047 - 19051 (2020)
Terminal uranium nitrides have so far proven impossible to isolate by photolysis of azides. Here we report the second ever example of an isolated terminal uranium(VI) nitride. We show that the terminal nitride [NBu4][U(OSi(OtBu)3)4(N)], 3, can be prepared upon photolysis with UV light of the U(IV) azide analogue. This is achieved by careful tailoring of the azide precursor and of the reaction conditions. Complex 3 is stable under ambient conditions but reacts readily with electrophiles (H+ and CO).
Synthesis of N-nitro-N′-(trimethylsilyl)carbodiimide
Churakov,Ioffe,Voronin,Tartakovsky
, (2017)
Nitration of N,N′-bis(trimethylsilyl)carbodiimide with N2O5 or (NO2)2SiF6 afforded N-nitro-N′-(trimethylsilyl)carbodiimide, the first representative of N-nitro carbodiimides. Its further nitration led
Efficient synthesis of trimethylsilyl pseudohalides catalyzed by PEG400/ZnI2 under ultrasound irradiation
Sufang, Wang,Shaobing, Wang,Yongshen, Xu
, p. 1271 - 1276 (2005)
Trimethylsilyl pseudohalides Me3SiX, where X = NCS, NCO, or CN, were readily prepared conveniently in desirable yields by the reaction of Me3SiCl with NaX or KX catalyzed by PEG400 and zinc iodide under ultrasound irradiation. Copyright Taylor & Francis, Inc.
Catalytic production of isocyanates via orthogonal atom and group transfers employing a shared formal group 6 M(II)/M(IV) redox cycle
Yonke, Brendan L.,Reeds, Jonathan P.,Fontaine, Philip P.,Zavalij, Peter Y.,Sita, Lawrence R.
, p. 3239 - 3242 (2014)
Under an atmosphere of CO, the Mo(IV) imido complex CpMo[N( iPr)C(Me)N(iPr)](NSiMe3) (Cp* = η5-C5Me5) (1) serves as a catalyst for production of an isocyanate via metal-mediated nitrene group transfer in benzene solution under mild conditions (55 °C, 10 psi) according to RN3 + CO → N2 + RNCO. Mechanistic and structural studies support a catalytic cycle for nitrene group transfer involving formal Mo(II) monocarbonyl and Mo(IV) (κ2-C,N)-isocyanate intermediates. These results complement an earlier finding that catalytic production of isocyanates can alternatively proceed through oxygen-atom transfer and an isomeric Mo(IV) (κ2-C,O)-isocyanate according to N2O + CNR → N2 + RNCO.
THE MOLECULAR STRUCTURE OF TRIMETHYLSILYLISOCYANATE IN THE GAS PHASE REDETERMINED BY ELECTRON DIFRACTION
Cradock, Stephen,Huntley, Christopher M.,Durig, J. R.
, p. 319 - 324 (1985)
We have redetermined the molecular structure of trimethylsilylisocyanate in the gas phase by electron diffraction.An ra structure is defined with bond distances (pm) SiN 174.0(4), SiC 186.4(2), N=C 120.2(16), C=O 117.6(10) and CH 109.9(5), bond angles (degrees) HCSi 109.0(9), CSiC 108.8(25), SiNC 156.9(30) and NCO 165.8(36), with the N=C bond eclipsing one Si-C bond and the Me3Si group tilted sligthly.The methyl groups are twisted 26.9(35) deg from the position giving the Me3Si group C3v symmetry in an (assumed) concerted fashion.The apparent deviations from linearity of the SiNCO skeleton are shown to be compatible with a pseudolinear structure similar to that of SiH3NCO.
New aspects of isocyanate synthesis with the use of O-silylurethanes
Kirilin, Aleksei D.,Belova, Liya O.,Pletneva, Maria V.,Golub, Nataliya A.,Storozhenko, Pavel A.,Kirilina, Nadezhda I.
, p. 99 - 100 (2017)
Silyl group at the nitrogen atom in the O-silylurethanes drastically affects the thermolysis processes and allows one to simplify the synthesis of methyl- and trimethylsilyl isocyanates.
Syntheses and characterizations of iron complexes of bulky: O -phenylenediamide ligand
Demuth, Joshua C.,Liang, Qiuming,Lin, Jack H.,Neidig, Michael L.,Song, Datong
, p. 12287 - 12297 (2020)
We report the syntheses of a family of tetrahedral iron complexes bearing a bulky redox active o-phenylenediamide ligand. The electronic structures of these complexes have been investigated by M?ssbauer spectroscopy, magnetic susceptibility measurements, and X-ray crystallography.
Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3
Bl?sing, Kevin,Bresien, Jonas,Maurer, Steffen,Schulz, Axel,Villinger, Alexander
supporting information, p. 1913 - 1920 (2021/05/10)
Me3Si?X (X=CN, N3, OCN, and SCN) was treated with the Lewis acids GaCl3 and B(C6F5)3 in toluene yielding the desired adducts Me3Si?X→GaCl3 and Me3Si?X→B(C6F5)3. All synthesized adducts were isolated and completely characterized including single crystal structure elucidations. The different structures, thermodynamics of formation and charge transfer effects are discussed on the basis of experimental and theoretical data.
Stoichiometric Reactions of CO2 and Indium-Silylamides and Catalytic Synthesis of Ureas
Xu, Maotong,Jupp, Andrew R.,Stephan, Douglas W.
supporting information, p. 14277 - 14281 (2017/10/31)
The indium compounds In(N(SiMe3)2)2Cl?THF (2) and In(N(SiMe3)2)Cl2?(THF)n (3) were shown to react with CO2 to give [(Me3Si)2N)InX(μ-OSiMe3)]2 (X=N(SiMe3)2 4, Cl 5). 0.05–2.0 mol % of the species 3 acts as a pre-catalyst for the conversion of aryl and alkyl silylamines under CO2 (2–3 atm) to give the corresponding ureas in 70–99 % yields. A proposed mechanism is supported by experimental and computational data.
