Stereochemical non-rigidity of N-(dimethylhalogenosilylmethyl)-N-(1-phenylethyl) acetamides in solutions

Negrebetsky, Vadim V.; Шипов, А. Г.; Крамарова, E. П.; Negrebetsky, Vitaliy V.; Baukov, Yuri I.

doi:10.1016/s0022-328x(96)06594-1

Cited by 19 publications

(12 citation statements)

References 18 publications

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“…This method does not require the knowledge of the mechanism of the ligand‐site exchange; however, it allows an understanding what substituent effects influence the free energies of activation Δ G ≠ . The Δ G ≠ values for 13 series, taken from the literature are given in Tables . In the majority of cases the free energies Δ G ≠ were calculated from the data on the coalescence of the NMR signals.…”

Section: Calculation Proceduresmentioning

confidence: 99%

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Ligand‐site exchange in intramolecular complexes of silicon: substituent effects

Кузнецова

Egorochkin

Negrebetsky

et al. 2012

J of Physical Organic Chem

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The intramolecular complexes containing coordination bonds Si←N or Si←O are distinguished for their stereochemical nonrigidity resulting in interconversion between isomers, that is, ligand‐site exchange. The influence of the substituents bound to the silicon atom on the free energies of activation for ligand exchange ΔG≠ of specific interest is poorly understood. In this work, the literature data on substituent influence on the energies ΔG≠ for 13 series of the complexes have been considered, using the correlation analysis. On the basis of the obedience of the energies ΔG≠ to the linear free energy relationship, it has been established for the first time that the ΔG≠ values depend not only on the inductive and resonance effects but also on the polarizability and steric effects of substituents. The reason for the occurrence of the polarizability effect is the appearance of excess charges on Si and N (or O) atoms as a result of intramolecular coordination consisting in the charge transfer from the donor center (N or O atom) to the acceptor one (Si atom). In some series the contribution of the polarizability or steric effect to the overall change in ΔG≠ because of the influence of substituents is a maximum. An understanding of these effects may give a better insight into the mechanism of nucleophilic substitution, involving organoelement compounds. Copyright © 2012 John Wiley & Sons, Ltd.

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Section: Calculation Proceduresmentioning

confidence: 99%

“…From the coalescence of these signals one can calculate the Δ G ≠ values . This approach has been developed in many publications . In specific cases (Table , Series IX, XII) the free energies Δ G ≠ are determined from results of NMR line‐shape analysis …”

Section: Calculation Proceduresmentioning

confidence: 99%

Ligand‐site exchange in intramolecular complexes of silicon: substituent effects

Кузнецова

Egorochkin

Negrebetsky

et al. 2012

J of Physical Organic Chem

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“…IR-spectra of compounds in solution and in the solid state were recorded on a Bruker Tensor-27 spectrometer using KBr cells and an APR element, respectively. 1 H, 13 29 Si NMR spectra were recorded using the 1 H- 29 Si HSQC pulse sequence supplied with the Bruker Avance II 600 instrument. 23 The 1 H, 13 C, 29 Si chemical shis were measured using Me 4 Si as internal reference.…”

Section: Methodsmentioning

confidence: 99%

“…1 H, 13 29 Si NMR spectra were recorded using the 1 H- 29 Si HSQC pulse sequence supplied with the Bruker Avance II 600 instrument. 23 The 1 H, 13 C, 29 Si chemical shis were measured using Me 4 Si as internal reference. The 19 F chemical shis were measured using BF 3 as external reference.…”

Section: Methodsmentioning

confidence: 99%

“…Mesyl and tosyl derivatives of (S)-proline, Ms-Pro-N(CH 2 -SiMe 2 ) 2 O (8a) and Ts-Pro-N(CH 2 SiMe 2 ) 2 O (8b), and mesyl derivative of sarcosine, MsN(Me)CH 2 C(O)N(CH 2 SiMe 2 ) 2 O (8c), were obtained by one-pot syntheses with yields of 75, 78 and 80%, respectively. The composition and structures of compounds 8 were conrmed by the elemental analysis, IR and multinuclear ( 1 H, 13 C, 29 Si and CP/MAS 29 Si) NMR spectroscopy. The structures of compounds 8a and 8c were also determined by X-ray method (see below).…”

Section: Synthesis Of Disilamorpholinesmentioning

confidence: 99%

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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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Hypervalent Silicon Compounds

Kost

Kalikhman

2009

Patai's Chemistry of Functional Groups

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Introduction Pentacoordinate Anionic Silicon Compounds Pentacoordinate Neutral Silicon Complexes Cationic Pentacoordinate Complexes Hexacoordinate Ionic Silicon Compounds Neutral Hexacoordinate Silicon Complexes Complexes with Higher Coordination Numbers Addendum

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Stereochemical non-rigidity of N-(dimethylhalogenosilylmethyl)-N-(1-phenylethyl) acetamides in solutions

Cited by 19 publications

References 18 publications

Ligand‐site exchange in intramolecular complexes of silicon: substituent effects

Ligand‐site exchange in intramolecular complexes of silicon: substituent effects

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

Hypervalent Silicon Compounds

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