2290-65-5Relevant articles and documents
THE MOLECULAR STRUCTURE OF TRIMETHYLSILYLISOTHIOCYANATE IN THE GAS PHASE, DETERMINED BY ELECTRON DIFFRACTION
Huntley, Christopher M.,Rankin, David W. H.,Robertson, Heather E.
, p. 103 - 110 (1987)
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.
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
Stewart, Constantine A.,Dickie, Diane A.,Parkes, Marie V.,Saria, Josephat A.,Kemp, Richard A.
experimental part, p. 11133 - 11141 (2011/02/16)
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.
Cyanogen formation during asymmetric cyanohydrin synthesis
Chechik, Victor,Conte, Marco,Dransfield, Trevor,North, Michael,Omedes-Pujol, Marta
supporting information; scheme or table, p. 3372 - 3374 (2010/08/07)
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.