- SuFEx Chemistry of Thionyl Tetrafluoride (SOF4) with Organolithium Nucleophiles: Synthesis of Sulfonimidoyl Fluorides, Sulfoximines, Sulfonimidamides, and Sulfonimidates
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Thionyl tetrafluoride (SOF4) is a valuable connective gas for sulfur fluoride exchange (SuFEx) click chemistry that enables multidimensional linkages to be created via sulfur–oxygen and sulfur–nitrogen bonds. Herein, we expand the available SuFEx chemistry of SOF4 to include organolithium nucleophiles, and demonstrate, for the first time, the controlled projection of sulfur–carbon links at the sulfur center of SOF4-derived iminosulfur oxydifluorides (R1?N=SOF2). This method provides rapid and modular access to sulfonimidoyl fluorides (R1?N=SOFR2), another array of versatile SuFEx connectors with readily tunable reactivity of the S?F handle. Divergent connections derived from these valuable sulfonimidoyl fluoride units are also demonstrated, including the synthesis of sulfoximines, sulfonimidamides, and sulfonimidates.
- Gao, Bing,Li, Suhua,Wu, Peng,Moses, John E.,Sharpless, K. Barry
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supporting information
p. 1939 - 1943
(2018/01/22)
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- THIONYL TETRAFLUORIDE MODIFIED COMPOUNDS AND USES
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Thionyl tetrafluoride gas reacts efficiently with primary amines to form reactive iminosulfur oxydifluoride compounds. These dual SVI-F loaded iminosulfur oxydifluoride compounds, in turn, readily react with secondary amines or aryloxy silyl ethers (ArO-SiR3), yielding the corresponding fused heteroatom-linked substrates. Iminosulfur oxyfluoride polymers also are provided by disclosed methods.
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Page/Page column 34
(2018/06/22)
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- Multidimensional SuFEx Click Chemistry: Sequential Sulfur(VI) Fluoride Exchange Connections of Diverse Modules Launched From An SOF4 Hub
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Sulfur(VI) fluoride exchange (SuFEx) is a new family of click chemistry based transformations that enable the synthesis of covalently linked modules via SVI hubs. Here we report thionyl tetrafluoride (SOF4) as the first multidimensional SuFEx connector. SOF4 sits between the commercially mass-produced gases SF6 and SO2F2, and like them, is readily synthesized on scale. Under SuFEx catalysis conditions, SOF4 reliably seeks out primary amino groups [R-NH2] and becomes permanently anchored via a tetrahedral iminosulfur(VI) link: R?N=(O=)S(F)2. The pendant, prochiral difluoride groups R?N=(O=)SF2, in turn, offer two further SuFExable handles, which can be sequentially exchanged to create 3-dimensional covalent departure vectors from the tetrahedral sulfur(VI) hub.
- Li, Suhua,Wu, Peng,Moses, John E.,Sharpless, K. Barry
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supporting information
p. 2903 - 2908
(2017/03/13)
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- Pentafluoronitrosulfane, SF5NO2
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The synthesis of pentafluoronitrosulfane, SF5NO2, is accomplished either by reacting N(SF5)3 with NO 2 or by the photolysis of a SF5Br/NO2 mixture using diazo lamps. The product is purified by treatment with CsF and repeated trap-to-trap condensation. The solid compound melts at -78°C, and the extrapolated boiling point is 9°C. SF5NO2 is characterized by 19F, 15N NMR, IR, Raman, and UV spectroscopy as well as by mass spectrometry. The molecular structure of SF 5NO2 is determined by gas electron diffraction. The molecule possesses C2v symmetry with the NO2 group staggering the equatorial S-F bonds and an extremely long 1.903(7) A S-N bond. Calculated bond enthalpies depend strongly on the computational method: 159 (MP2/6-311G++(3df)) and 87 kJ mol-1 (B3LYP/6-311++G-(3df)). The experimental geometry and vibrational spectrum are reproduced reasonably well by quantum chemical calculations.
- Lu, Norman,Thrasher, Joseph S.,Von Ahsen, Stefan,Willner, Helge,Hnyk, Drahomir,Oberhammer, Heinz
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p. 1783 - 1788
(2008/10/09)
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- Quantitative infrared spectroscopic analysis of SF6 decomposition products obtained by electrical partial discharges and sparks using PLS-calibrations
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Infrared spectroscopy is a powerful tool for the analysis of gaseous by-products in sulfur hexafluoride gas used as an insulator in high-voltage equipment. Sparks and electrical partial discharges were generated between different point-plane configurations within a custom-made discharge chamber constructed from stainless steel and Teflon. Various electrode materials were used such as stainless steel, copper, aluminium, silver, tungsten and tungsten/copper alloy. Owing to the different electrical conditions, a wide concentration range of the decomposition products existed. The main-products found were the sulfuroxyfluorides SOF4 and SOF2, as well as HF following experiments with partial discharges and sparking with energies around 1.0 J/spark. All infrared spectra were recorded using an FTIR-spectrometer equipped with a 10 cm gas cell. Quantification was carried out using classical least-squares and partial least-squares (PLS) with multivariate spectral data from selected intervals. PLS calibration models were also optimised under the constraint of a minimum number of spectral variables with a view to developing simple photometers based on a restricted number of laser wavelengths. Standard errors of prediction obtained by cross-validation of different PLS calibration models are reported for the compounds mentioned, as well as for SF4, SO2F2 and SiF4.
- Kurte,Heise,Klockow
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p. 505 - 513
(2007/10/03)
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- Rate Constants For F- Transfer from SF6- to Fluorinated Gases and SO2. Temperature Dependence and Implications or Electrical Discharges in SF6
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The reactivity of SF6- toward SO2, SOF2, SO2F2, SOF4, SF4, and SiF4 has been investigated by using the technique of pulsed electron beam high-pressure mass spectrometry.These studies were initiated in order to probe the complex anionic chemistry occuring during electrical discharge in SF6.Although no reaction of any type was observed with SOF2 and SO2F2, efficient F- transfer of the type SF6- + A --> AF- + SF5 was found in all of the other systems including the SO2F- + SOF4 pair, which was studied separately.With the exception of the SF6- + SiF4 reaction, all of the pairs exhibited a negative temperature coefficient in that the rate constants for F- transfer decreased substantially with increasing temperature.The reaction SF6- + SiF4 --> SiF5- + SF5 was found to proceed with a rate constant of (5.6 +/-0.8)E-10 cm3/(molecule*s) throughout the temperature range studied (298-510 K), which corresponds to a collision efficiency of unity.The other reactions were found to approach unit collision efficiency only at reduced temperatures (- affinity scale, and the F- affinity of SiF4 was defined as 2.2 +/-0.4 kcal/mol higher than SOF4 via equilibria measurements.The placement of SF5 within the F- affinity scale indicates that SF6- is reactive toward several of the major stable byproducts generated during electrical breakdown in SF6.This behavior was verified by direct observation of the temporal growth and decay profiles of the various anions produced after pulsed ionization of an SF6 sample which had been subjected to prior partial decomposition in a negative corona discharge.Some comments are also included concerning the stability of the SF6-*SF6 dimer ion, and the implications of all of the present data with respect to mobility measurements in SF6 are also discussed.
- Sieck, L. Wayne,Brunt, Richard J. Van
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p. 708 - 713
(2007/10/02)
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