On the question of complexation of silatranes with tetracyanoethylene

Pestunovich, V. A.; Petukhov, L. P.; Vakul’skaya, T. I.; Baryshok, V. P.; Turchaninov, V. K.; Frolov, Yu. L.; Воронков, М. Г.

doi:10.1007/bf00923416

Cited by 2 publications

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“…Judging by the positive Δ G c values, the complexes of 1a – c with CHCl 3 and CH 3 OH in any composition are not stable (Figure ) . However, according to the MP2/6-311++G(3df,3pd) single point calculations, they may exist at low temperatures (Figure ).…”

Section: Resultsmentioning

confidence: 96%

Correlation among the Gas-Phase, Solution, and Solid-Phase Geometrical and NMR Parameters of Dative Bonds in the Pentacoordinate Silicon Compounds. 1-Substituted Silatranes

Belogolova

Sidorkin

2013

J. Phys. Chem. A

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Silatranes XSi(OCH2CH2)3N exhibit a good linear relationship between their experimental and calculated (IGLO and GIAO) values of the NMR chemical shifts of (15)N, δN, and the lengths of dative bonds Si←N, dSiN, determined in the gas phase (ED, CCSD), solutions (COSMO PBE0, B3PW91), and crystals (X-ray). An aggregate of the obtained data provides strong evidence that the gas-phase value of dSiN in MeSi(OCH2CH2)3N should be greater by ∼0.05 Å than that determined in the electron diffraction (ED) experiment (2.45 Å). Given this condition, a long-standing contradiction between the data of the structural (X-ray, ED) and NMR (15)N experiments for the molecules of 1-methyl- and 1-fluorosilatrane regarding the sensitivity of their coordination contact Si←N to the medium effect is resolved.

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Section: Resultsmentioning

confidence: 96%

Correlation among the Gas-Phase, Solution, and Solid-Phase Geometrical and NMR Parameters of Dative Bonds in the Pentacoordinate Silicon Compounds. 1-Substituted Silatranes

Belogolova

Sidorkin

2013

J. Phys. Chem. A

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“…First, in contrast with fourcoordinate analogs and many pentacoordinate organosilicon compounds, silatranes display low activity in nucleophilic substitution reactions at the silicon. The in-oriented nitrogen atom appears to be inert toward electrophiles such as MeI 13 and tetracyanoethylene 293 . The strong electron-releasing effect combined with the large bulk of the silatranyl group affect the reactivity of the exocyclic groups of these compounds.…”

Section: Introductionmentioning

confidence: 98%