DATASET FOR: Solvents Promote Selective TEDA2+. Formation Driven through a Pnicogen Bond in Selectfluor
Description
This data presents evidence of decomposition of Selectfluor in solution, increased as solvent donor nature increases. Evidence is based on NMR (1H-NMR and 19F-NMR) and EPR data in different solvents. Titration of Selectfluor with solvents in presented. 19-FNMR spectra for association between Selectfluor-solvent is shown for DMF, acetonitrile and acetone. Data for theoretical calculations of complexation between Selectfluor and solvent (1, 2 or 3 solvent molecules) are shown. Document .log and .fchk for each complexation is presented. The work plans the decomposition of Selectfluor in solution, which is promoted by a pnicogen bond. Data for decomposition (NMR and EPR), for association binding (titration from 19F-NMR) and definition of modes of interaction through DFT-calculations.
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NMR experiments: For determination of association constant, each 1H-NMR experiment, 2 mg of Selectfluor (SF) in 0.5 mL of D2O (~22 mM) was mixed with varying amounts of the tested solvent (H) (e.g. DMF or acetonitrile) from 50 to 8800 mM. The solvent amounts were transferred to NMR tube containing Selectfluor solution using solvent solution of 10, 20, 30, 40, 50, 60, 70, 80 and 90 µL. The NMR tube was inverted several times until Selectfluor was dissolved, then a sealed capillary of TFE was placed in the NMR tube as an internal standard, (δ 77.663 ppm in 19F-NMR). The chemical shifts for the N-F fluorine upon different solvent amount were collected and tabulated in an excel document . On other hand, from NMR analysis, herein we verified the decomposition of the Selectfluor under any solvent environment, 1H-NMR spectra of the Selectfluor (5-10 mg/0.5mL acetone-d6) in presence of 50-100 µL of DMF or acetonitrile were collected at room-temperature (298 K) at time 0 hours. DFT calculations. All theoretical calculations, in the gas phase, were performed using density functional theory (DFT) with the Gaussian 09 quantum chemistry software [2]. M06-2X functional [3] in combination with the def2TZVP basis set [4] were employed. The geometries of the Selectfuor, acetonitrile, acetone and water were optimized. All structures were optimized in the ground state without restrictions, using tight optimization criteria and an ultrafine grid in the computation of two-electron integrals and their derivatives. Optimization calculations were performed using the Berny algorithm and were successfully completed with the following parameters: maximum force, 0.000450; root-mean-square (RMS) force, 0.000300; maximum displacement, 0.001800; RMS displacement, 0.001200; predicted change in energy, −1.488276×10−8 Hartree for most of studied cases. Complexation calculations to predict the most probable complexes between specific solvent (acetonitrile, acetone and water) with Selectfluor were performed using counterpoise (CP) method taken into consideration basis set superposition error (BSSE) approach[5]. Harmonic vibrational frequential analyses was performed for all studied adducts at the same level of theory. EPR measurements. These measurements were performed following reported protocol with a few modifications [9]. A solution of selectfluor (0.6 mmol, 212.5 mg) in degassed dry CH3CN, DMF, acetone, methanol, water or BF4-BMIM (2.0 mL) were stirred under nitrogen atmosphere. Then, DMPO (30 μL) was added into the reaction system at 25 ˚C. The solution sample was taken out into a small tube and analyzed by EPR. EPR spectra was recorded at room temperature on EPR spectrometer operated at 9.821452 GHz. Typical spectrometer parameters are shown as follows, scan range: 150 G; center field set: 3504.54 G; time constant: 163.84 ms; scan time: 30 s modulation amplitude: 1.0 G; modulation frequency: 100 kHz; receiver gain: 1.00×104; microwave power: 21.59.
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