Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides*

Nikolin, A. A.; Arkhipov, Dmitry E.; Шипов, А. Г.; Крамарова, E. П.; ̇ˈchuk, N. A. Koval; Korlyukov, Alexander A.; Negrebetsky, Vadim V.; Baukov, Yu. I.; Bassindale, Alan R.; Taylor, Peter G.; Bowden, Allen A.; Bylikin, S. Yu.

doi:10.1007/s10593-012-0949-7

Cited by 18 publications

(3 citation statements)

References 30 publications

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“…Disiloxanes 1a−f were synthesized according to published procedures. 34 Fluorosilanes 2a−f were prepared as follows. A solution of disiloxane 1a−f (1 mmol) in acetonitrile (5 mL) was refluxed with Et 2 O•BF 3 (0.11 g, 0.8 mmol) for 2 h and cooled, and the volatiles were removed in vacuo.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis, Structures, and Stereodynamic Behavior of Novel Pentacoordinate Fluorosilanes: Fluorosilyl Derivatives of Proline

et al. 2012

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were synthesized from the corresponding disiloxanes 1a−f using Et 2 O•BF 3 . According to the NMR and IR data, the extent of dimerization of fluorosilanes 2a−f in solution is negligible, while the O→Si coordination in solution is weaker than that in the solid state. Comparative CP/MAS NMR and X-ray diffraction studies revealed that in solution the coordination Si−O bond length varies in a narrow range (2.22−2.24 Å) that is 0.02−0.11 Å longer than in the crystalline state. Dynamic NMR (DNMR) studies of the fluorides revealed a fine structure of the 19 F signals in the 0−20 °C temperature range, which was related to the structural features of the coordination set in these complexes. The temperature dependence of the SiMe 2 signals in the 1 H DNMR spectra was attributed to a permutational isomerization process involving a positional exchange of equatorial ligands. The narrow range of activational barriers of the process (23−24 kcal mol −1 and more) and high negative values of the entropy of activation are similar to those observed earlier for Si-substituted N-(dimethylsilylmethyl) and N-(methylphenylsilylmethyl) amides and lactams, which suggests similar permutational processes in all cases. Gas-phase quantum chemical studies demonstrate that the solvation of F − reduces the activation barrier.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis, Structures, and Stereodynamic Behavior of Novel Pentacoordinate Fluorosilanes: Fluorosilyl Derivatives of Proline

et al. 2012

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“…Ethyl esters of N-mesyl-(S)-proline and N-tosyl-(S)-proline were synthesised as described earlier. 10…”

Section: Methodsmentioning

confidence: 99%

N,N-Bis-(dimethylfluorosilylmethyl)amides of N-organosulfonylproline and sarcosine: synthesis, structure, stereodynamic behaviour and in silico studies

et al. 2016

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“…This is somewhat surprising, since the compounds of hypervalent silicon normally show enhanced reactivity in reactions with both electrophiles and nucleophiles . A hydrolysis reaction is not an exception; according to theoretical and experimental data, the pentacoordinated silicon compounds with different types of coordination (silatranes and O→Si chelates), including pentacoordinated fluorosilanes, react with water . N‐(Silylmethyl)phosphoramides R 2 P(O)NR′CH 2 SiMe 3–n Hal n having relatively weak coordination bond P=O→Si (2.1 < d SiO < 2.7 Å) give complexes with chloroform .…”

Section: Introductionmentioning

confidence: 99%

Effect of proton donors on the intramolecular coordination C=O→Si-F in (acyloxymethyl)trifluorosilanes.Ab initio,DFT and FTIR study, QTAIM analysis

Chípanina

Lazareva

Aksamentova

et al. 2014

J. Phys. Org. Chem.

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The intramolecular С=O→Si coordination in H‐complexes of (acetoxymethyl)trifluorosilane and (benzoyloxymethyl)trifluorosilane with proton donors HCl, PhOH, MeOH, and CHCl3 was investigated by density functional theory and second‐order Møller‐Plesset perturbation theory (MP2) methods. Interrelation and mutual influence of the intramolecular coordination bond С=O→Si and intermolecular hydrogen bonds C=O···H and Si–F···H in H‐complexes was established using the AIM and NBO analyses. The С=O→Si coordination is weakened by the C=O···H hydrogen bonding but enhanced by the Si–Fax···H hydrogen bonding. The structure of H‐complexes of (acetoxymethyl)trifluorosilane with proton donors in solution was determined by comparing the ν(C=O) and ν(Si–F) frequencies calculated using the conductor‐like polarizable continuum model and their experimental Fourier transform infrared values. Copyright © 2014 John Wiley & Sons, Ltd.

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Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides*

Cited by 18 publications

References 30 publications

Synthesis, Structures, and Stereodynamic Behavior of Novel Pentacoordinate Fluorosilanes: Fluorosilyl Derivatives of Proline

Synthesis, Structures, and Stereodynamic Behavior of Novel Pentacoordinate Fluorosilanes: Fluorosilyl Derivatives of Proline

N,N-Bis-(dimethylfluorosilylmethyl)amides of N-organosulfonylproline and sarcosine: synthesis, structure, stereodynamic behaviour and in silico studies

Effect of proton donors on the intramolecular coordination C=O→Si-F in (acyloxymethyl)trifluorosilanes.Ab initio,DFT and FTIR study, QTAIM analysis

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