- POLYSULFONYLAMINE: TEIL LXXI. EIN MOLEKUEL MIT EINER LANGEN Si(sp3)-O-BINDUNG: SYNTHESE, STRUKTUR UND REAKTIVITAET VON N,N-DIMESYLAMIDOSCHWEFELSAEURETRIMETHYLSILYLESTER
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The title compound (MeSO2)2N-SO2-O-SiMe3 (2; m.p. 57 deg C) is obtained by treating (MeSO2)2N-SiMe3 (3) with one equivalent of sulfur trioxide in CH2Cl2 at -20 deg C.The crystal structure of 2 (triclinic, space group P) was established by low-temperature X-ray diffraction.The most interesting feature of the molecular structure is the geometry of the S-O-Si sequence, displaying a very long Si(sp3)-O bond, a short S(sp3)-O bond and a large angle at oxygen (mean values for two independent molecules: Si-O 174.1, S-O 151.1 pm, S-O-Si 134.3 deg).The coordination at nitrogen is trigonal-planar (S-N-S 118.5-121.0 deg, S-N 170.5-173.1 pm). 2 is instantaneously hydrolyzed by excess water to form (MeSO2)2NH, sulfuric acid and (Me3Si)2O.In vacuo at 60 deg C, molten 2 will readily dissociate into its precursors 3 and SO3.It is shown that 2 may react either as an SO3 donor or as a sulfosilylating reagent.Reaction with Lewis bases such as Me3N, pyridine or R2PCl (R = tBu, Ph) proceeds with the formation of the corresponding complexes B*SO3; thermolysis of the isolable phosphane complexes affords the respective phosphane oxides R2(Cl)PO.Sulfosilylation of phenol, cyclohexene or 2,3-dimethyl-2-butene with 2 in CH2Cl2 gives the trimethylsilyl esters of 4-hydroxybenzenesulfonic, cyclohexene-3-sulfonic, or 2,3-dimethyl-1-butene-3-sulfonic acids, respectively.Key words: Trimethylsilyl N,N-dimesylamidosulfonate, synthesis, X-ray structure, long Si(sp3)-O bond, SO3 transfer, sulfosilylation.
- Hiemisch, Oliver,Blaschette, Armand,Jones, Peter G.
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p. 161 - 172
(2007/10/03)
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- Hydrogen Halide Radical Anions
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Exposure of Me3NSO3 doped with Me3NHX (X = F, Cl Br, or I) to 60Co γ-rays at 77 K gives radicals whose e.s.r. spectra show hyperfine coupling to 1H and X nuclei.These are identified as HX.- radical anions.The species HF.- has properties of normal trapped hydrogen atoms, but the remainder are thought to be genuine radical anions with a ?* semi-occupied molecular orbital.The HCl.- and HBr.- radicals rotate about a specific axis normal to the ? bond at 77 K but the motion is quenched on further cooling.Possible mechanisms for the radiolytic processes are discussed.Other radicals detected during the course of the work include SO3.-, Me3N.+, and H2C.NMe2SO3.
- Raynor, J. Barrie,Rowland, Ian J.,Symons, Martyn C. R.
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p. 421 - 426
(2007/10/02)
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