- THE MOLECULAR STRUCTURE OF TRIMETHYLSILYLISOTHIOCYANATE IN THE GAS PHASE, DETERMINED BY ELECTRON DIFFRACTION
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The structure of gaseous trimethylsilylisothiocyanate has been redetermined by electron diffraction.In the ra structure, the bondlengths are Si-C 186.6(3), Si-N 174.3(6), N=C 119.1(6), C=S 158.7(4) and C-H 110.0(5) pm, and the angles are NSiC 108.8(7), SiNC 158.2(10) and SiCH 108.9(8) deg.There is a small apparent deviation from linearity (ca. 4 deg) in the NCS group, but it is likely that the SiNCS skeleton is pseudolinear, as is in related molecules.
- Huntley, Christopher M.,Rankin, David W. H.,Robertson, Heather E.
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Read Online
- Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3
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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.
- Bl?sing, Kevin,Bresien, Jonas,Maurer, Steffen,Schulz, Axel,Villinger, Alexander
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supporting information
p. 1913 - 1920
(2021/05/10)
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- Pseudohalonium ions: [Me3Si-X-SiMe3]+ (X = CN, OCN, SCN, and NNN)
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By utilizing reaction mixtures, such as Me3Si-XV[Me 3Si-X-SiMe3]+ (X = CN, OCN, SCN, and NNN), it was possible to prepare the first examples of bissilylated pseudohalonium cations in high yields. The structure and bonding of a whole series of salts containing pseudohalonium cations is discussed on the basis of experimentally observed (X-ray diffraction, Raman, and IR spectroscopy, and mass spectrometry) and theoretically obtained data. Salts containing pseudohalonium cations are only stable in the presence of weakly coordinating anions, such as the well-known tetrakis(pentafluorophenyl)borate, [B(C6Fs) 4]-.
- Schulz, Axel,Villinger, Alexander
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supporting information; experimental part
p. 7276 - 7281
(2010/09/16)
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- Reactivity of bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin with CO2, OCS, and CS2 and comparison to that of bis[bis(trimethylsilyl)amido]tin
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The heterocumulenes carbon dioxide (CO2), carbonyl sulfide (OCS), and carbon disulfide (CS2) were treated with bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin {[(CH 2)Me2Si]2N}2Sn, an analogue of the well-studied bis[bis(trimethylsilyl)amido]tin species [(Me3Si) 2N]2Sn, to yield an unexpectedly diverse product slate. Reaction of {[(CH2)Me2Si]2N}2Sn with CO2 resulted in the formation of 2,2,5,5-tetramethyl-2,5-disila-1- oxacyclopentane, along with Sn4(μ4-O){μ2- O2CN[SiMe2(CH2)2]} 4(μ2-N=C=O)2 as the primary organometallic Sn-containing product. The reaction of {[(CH2)Me2Si] 2N}2Sn with CS2 led to formal reduction of CS2 to [CS2]2-, yielding [{[(CH 2)Me2Si]2N}2Sn]2CS 2{[(CH2)Me2Si]2N}2Sn, in which the [CS2]2- is coordinated through C and S to two tin centers. The product [{[(CH2)Me2Si]2N} 2Sn]2CS2{[(CH2)Me 2Si]2N}2Sn also contains a novel 4-membered Sn-Sn-C-S ring, and exhibits a further bonding interaction through sulfur to a third Sn atom. Reaction of OCS with {[(CH2)Me2Si] 2N}2Sn resulted in an insoluble polymeric material. In a comparison reaction, [(Me3Si)2N]2Sn was treated with OCS to yield Sn4(μ4-O)(μ2- OSiMe3)5(n1-N=C=S). A combination of NMR and IR spectroscopy, mass spectrometry, and single crystal X-ray diffraction were used to characterize the products of each reaction. The oxygen atoms in the final products come from the facile cleavage of either CO2 or OCS, depending on the reacting carbon dichalogenide.
- Stewart, Constantine A.,Dickie, Diane A.,Parkes, Marie V.,Saria, Josephat A.,Kemp, Richard A.
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experimental part
p. 11133 - 11141
(2011/02/16)
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- Cyanogen formation during asymmetric cyanohydrin synthesis
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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.
- Chechik, Victor,Conte, Marco,Dransfield, Trevor,North, Michael,Omedes-Pujol, Marta
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supporting information; scheme or table
p. 3372 - 3374
(2010/08/07)
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- Efficient synthesis of trimethylsilyl pseudohalides catalyzed by PEG400/ZnI2 under ultrasound irradiation
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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.
- Sufang, Wang,Shaobing, Wang,Yongshen, Xu
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p. 1271 - 1276
(2007/10/03)
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- A study on the haterogeneous reaction of trialkylsilyl chlorides with inorganic salts and monocarboxylates catalysed by PEG400
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The important and useful trialkylsilyl pseudohalides R3SiX, where X=NCS, NCO, N3 or CN and R=methyl or ethyl, and trimethylsilyl monocarboxylates, where X=RCOO, were readily prepared in high yields by nucleophilic substitution of R3SiCl with X ions provided by NaX or KX at room temperature catalysed by PEG400 and zinc iodide. The reactions of trimethylsilyl chloride with some metal oxysalts were also studied for the first time.
- Du, Yun-Fei,Cao, Yu-Qing,Dai, Zhi,Chen, Bao-Hua
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p. 223 - 225
(2007/10/03)
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- REACTION OF BIS-- AND BIS--DISULFIDES WITH TRIALKYLSILYLCYANIDES. NEW ROUTE TO DIALKYLPHOSPHORO- AND DIALKYLTHIOPHOSPHORO THIOCYANIDATES AND O,O,O,O-TETRAALKYLPYROPHOSPHOROTRITHIOATES
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The reaction of organophosphorus disulfides with trialkylsilylcyanide has been investigated.It provided direct evidence for the intermediacy of thiocyanidate >P(X)SCN, X=O, S in this type of reaction.The disulfides studied involved phosphoryl, phosphonyl and/or phosphinyl disulfides.They have been shown to follow the common mechanism.The studied reaction of thiophosphoryl disulfides with trimethylsilylcyanide represents a new and highly efficient route to tetraalkylpyrophosphorotrithioates.
- Lopusinski, Andrzej,Luczak, Lech,Brzezinska, Ewa
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p. 101 - 108
(2007/10/02)
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- Substitution Reaction of Organic Halide by Trimethylsilyl Isothiocyanate: Formation of Thiocyanate and Its Rearrangement to Isothiocyanate
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The reaction of organic halide with trimethylsilyl isothiocyanate (TMSTC) gave thiocyanate 1 and its isomerized isothiocyanate 2.Details of the substitution and the isomerization reactions were examined.
- Nishiyama, Kozaburo,Oba, Makoto
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p. 2692 - 2694
(2007/10/02)
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- ULTRAVIOLET SPECTROSCOPIC INVESTIGATION OF ISOCYANATO- AND ISOTHIOCYANATO SILANES CONTAINING PHENYL- AND METHYL GROUPS
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The members of the series R(n)Si(NCO)(4-n) and R(n)Si(NCS)(4-n), where R = -CH3 and -C6H5, were prepared, their ultraviolet spectra recorded and the observed bands assigned.The spectra were compared to those of halogeno derivatives.The similarity of halogen- and pseudohalogeno-groups and difference between the effect of methyl- and phenyl-groups were studied.
- Veszpremi, Tamas,Barta, Istvan,Nagy, Jozsef
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p. 243 - 250
(2007/10/02)
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- RING OPENING REACTIONS OF THIIRANES WITH GROUP IV B ORGANOMETALLICS: A NEW REGIOSELECTIVE ROUTE TO β-AMINO AND β-CYANIDE THIOLS.
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Regioselective opening of the thiirane ring occurs spontaneously with Group IV B organometallics such as Me3SnNR2 and under the catalytic action of AlCl3 with Me3SiCN, affording difunctional thiols.
- Taddei, Maurizio,Papini, Annamaria,Fiorenza, Mariella,Ricci, Alfredo,Seconi, Giancarlo
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p. 2311 - 2314
(2007/10/02)
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