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- conformational analysis (2)
- dynamic NMR (2)
- quantum chemical calculations (2)
- 1,3-Azasilinanes (1)
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- 1,4,2-Oxazasilinanes (1)
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- Institut für Chemie (14)
Two novel and simple approaches to N-triflyl guanidines are elaborated. Owing to very strong conjugation the formally double C=N bond of TIN=C(NHR)(2) is longer than the formally single N-C bonds. Energetic effect of the triflylgroup on the conjugation in the N-C=N moiety is estimated to be >= 150 kcal/mol.
4,4-Dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane 1 and 2,2,6,6-tetramethyl-4-(trifluoromethylsulfonyl)- 1,4,2,6-oxazadisilinane 2 were studied by variable temperature dynamic 1H, 13C, 19F NMR spectroscopy and theoretical calculations at the DFT (density functional theory) and MP2 (Moller-Plesset 2) levels of theory. Both kinetic (barriers to ring inversion) and thermodynamic data (frozen conformational equilibria) could be obtained for the two compounds. The computations revealed two minima on the potential energy surface for molecules 1 and 2 corresponding to the rotamers with the CF3SO2 group directed inward and outward the ring, the latter being 0.20.4 kcal/mol (for 1) and 1.1 kcal/mol (for 2) more stable than the former. The vibrational calculations at the DFT and MP2 levels of theory give the values of the free energy difference Delta G degrees for the 'inward' reversible arrow 'outward' equilibrium consistent with those determined from the experimentally measured ratio of the rotamers. The structure of crystalline compound 2 was ascertained by X-ray diffraction analysis.
4,4-Dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane 1 and 2,2,6,6-tetramethyl-4-(trifluoromethylsulfonyl)-1,4,2,6-oxazadisilinane 2 were studied by variable temperature dynamic 1H, 13C, 19F NMR spectroscopy and theoretical calculations at the DFT (density functional theory) and MP2 (Moller-Plesset 2) levels of theory. Both kinetic (barriers to ring inversion) and thermodynamic data (frozen conformational equilibria) could be obtained for the two compounds. The computations revealed two minima on the potential energy surface for molecules 1 and 2 corresponding to the rotamers with the CF3SO2 group directed inward and outward the ring, the latter being 0.20.4 kcal/mol (for 1) and 1.1 kcal/mol (for 2) more stable than the former. The vibrational calculations at the DFT and MP2 levels of theory give the values of the free energy difference Delta G degrees for the 'inward' reversible arrow 'outward' equilibrium consistent with those determined from the experimentally measured ratio of the rotamers. The structure of crystalline compound 2 was ascertained by X-ray diffraction analysis.
The conformational equilibria of 1-phenyl-1-silacyclohexane 1, 3-phenyl-1,3-thiasilacyclohexane 2, 1-methyl-1- phenyl-1-silacyclohexane 3, and 3-methyl-3-phenyl-1,3-thiasilacyclohexane 4 have been studied for the first time by low temperature C-13 NMR spectroscopy at 103 K. Predominance of the equatorial conformer of compound 1 (Ph-eq/Ph-ax=78%:22%) is much less than in its carbon analog, phenylcyclohexane (nearly 100% of Ph-eq). And in contrast to 1-methyl-1- phenylcyclohexane, the conformers with the equatorial Ph group are predominant for compounds 3 and 4: at 103 K, Ph-eq/Ph- ax ratios are 63%:37% (3) and 68%:32% (4). As the Si-C bonds are elongated with respect to C-C bonds, the barriers to ring inversion are only between 5.2-6.0 (ax -> eq) and 5.4-6.0 (eq -> ax) kcal mol(-1). Parallel calculations at the DFT and MP2 level of theory (as well as the G2 calculations for compound 1) show qualitative agreement with the experiment. The additivity/nonadditivity of conformational energies of substituents on cyclohexane and silacyclohexane derivatives is analyzed. The geminally disubstituted cyclohexanes containing a phenyl group show large deviations from additivity, whereas in 1-methyl-1-phenyl-1-silacyclohexane and 3-methyl-3-phenyl-1,3-thiasilacyclohexane the effects of the methyl and phenyl groups are almost additive. The reasons for the different conformational preferences in carbocyclic and heterocyclic compounds are analyzed using the homodesmotic reactions approach.
The conformational equilibria of 1-phenyl-1-silacyclohexane 1, 3-phenyl-1,3-thiasilacyclohexane 2, 1-methyl-1-phenyl-1-silacyclohexane 3, and 3-methyl-3-phenyl-1,3-thiasilacyclohexane 4 have been studied for the first time by low temperature C-13 NMR spectroscopy at 103 K. Predominance of the equatorial conformer of compound 1 (Ph-eq/Ph-ax=78%:22%) is much less than in its carbon analog, phenylcyclohexane (nearly 100% of Ph-eq). And in contrast to 1-methyl-1-phenylcyclohexane, the conformers with the equatorial Ph group are predominant for compounds 3 and 4: at 103 K, Ph-eq/Ph-ax ratios are 63%:37% (3) and 68%:32% (4). As the Si-C bonds are elongated with respect to C-C bonds, the barriers to ring inversion are only between 5.2-6.0 (ax -> eq) and 5.4-6.0 (eq -> ax) kcal mol(-1). Parallel calculations at the DFT and MP2 level of theory (as well as the G2 calculations for compound 1) show qualitative agreement with the experiment. The additivity/nonadditivity of conformational energies of substituents on cyclohexane and silacyclohexane derivatives is analyzed. The geminally disubstituted cyclohexanes containing a phenyl group show large deviations from additivity, whereas in 1-methyl-1-phenyl-1-silacyclohexane and 3-methyl-3-phenyl-1,3-thiasilacyclohexane the effects of the methyl and phenyl groups are almost additive. The reasons for the different conformational preferences in carbocyclic and heterocyclic compounds are analyzed using the homodesmotic reactions approach.
Structure and the conformational properties of 1,3,3-trimethyl-1,3-azasilinane have been studied. According to gas electron diffraction (GED), the molecule exists in a slightly distorted chair conformation with the N-Me group in equatorial position. High-level quantum chemical calculations excellently, reproduce the experimental geometry. Employing variable temperature H-1 and C-13 NMR spectroscopy down to 103 K, the conformational equilibrium could be frozen and the barrier to ring inversion determined.
1-Isopropyl-3-methyl-3-phenyl-1,3-azasilinane 1 and 1-isopropyl-3,3-dimethyl-1,3-azasilinane 2 were synthesized and a detailed analysis of their NMR spectra, conformational equilibria and ring inversion processes is presented. Low temperature H-1/C-13 NMR spectroscopy, iteration of the H-1 NMR spectra and quantum chemical calculations showed slight predominance of the PheqMeax over the PhaxMeeq conformer of 1 at low temperature. The barrier for the chair to chair interconversion of both compounds was measured to be 8.25 kcal/mol.
1,3-Dimethyl-3-phenyl-1,3-azasilinane was synthesized and its conformational behavior was studied by the low temperature NMR spectroscopy and quantum chemical calculations. The compound was shown to exist as an equilibrium mixture of the PhaxMeeq and PheqMeax chair conformers with the N-methyl substituent in equatorial position. The barrier to ring inversion was also determined.
A silicon analog of quinolizidine 3,3,7,7-tetramethylhexahydro-1H-[1,4,2]oxazasilino[4,5-d][1,4,2]oxazasilin-9a-yl)methanol 3 was synthesized. X-ray diffraction analysis confirmed the trans configuration and low temperature NMR spectroscopy both the flexibility (barrier of interconversion 5.8 kcal mol(-1)) and the conformational equilibrium (chair-chair and chair-twist conformers) of the compound. The relative stability of the different isomers/conformers of 3 was calculated also at the MP2/6-311G(d,p) level of theory. Intra- and intermolecular hydrogen bonding in 3 and the appropriate equilibrium between free and self-associated molecules was studied in solvents of different polarity. Both the N-methyl quaternary ammonium salt and the O-trimethylsilyl derivative of 3 could be obtained and their structure determined.
A number of N-substituted 2,2-dimethyl-1,4,2-oxazasilinanes 1 were synthesized and studied by variable temperature dynamic H-1 and C-13 NMR spectroscopy, room temperature N-15 NMR spectroscopy and theoretical calculations at the DFT and MP2 levels of theory. Both the preferred conformers were assigned and the barrier to the ring inversion of the saturated six-membered ring determined. From 1 the corresponding methyl iodide salts were produced, their structure studied by X-ray analysis and found to be in excellent agreement with the results of the theoretical calculations.
The conformational analysis of the first representative of the Si-alkoxy substituted six-membered Si,N-heterocycles, 1,3-dimethyl-3-isopropoxy-3-silapiperidine, was performed by low-temperature 1H and 13C NMR spectroscopy and DFT theoretical calculations. In contrast to the expectations from the conformational energies of methyl and alkoxy substituents, the Meaxi-PrOeq conformer was found to predominate in the conformational equilibrium in the ratio Meaxi-PrOeq : Meeqi-PrOax of ca. 2 : 1 as from the 1H and 13C NMR study. The thermodynamic parameters obtained by the complete line shape analysis showed that the main contribution to the barrier to ring inversion originates from the entropy term of the free energy of activation.