Новосибирский институт органической химии им. Н.Н. Ворожцова СО РАН

Лаборатория изучения механизмов органических реакций

Nice Merry-Go-Round of Trisilyl-Substituted Vinyl Cation

Andrea Klaer, Yvonne Syha, Hamid Reza Nasiri, and Thomas Müller. Chem. Eur. J. 2009, 15, 8414-8423.
DOI: 10.1002/chem.200900795



Energy (without ZPE) and geometry by DFT/PBE/L1 (cc-pVDZ) (PRIRODA program).

Click to energy level to view 3D structure (run Jmol java-applet). Click to level inscription to download or open xyz coordinates file.
12.35 12.35 2.04 2.04 2.04 2.04 0.25 0.25 0.00 0.00 0.00 0.00
Experimental EA 56.0±3.3 kJ/mole

gif animation of IRC (step 0.4 Å·amu½)


Download IRC in xyz format

1b or 1b-MP2 ?

Experimental and calculated (DFT/PBE/L22) 13C NMR chemical shifts of 1b Cα and Cβ atoms



Equilibrium 1b ⇄ 1b-MP2 or very flat PES with single minimum. Temperature dependence of Cα and Cβ chemical shifts is expected.

Theoretical model for threefold degenerate merry-go-round of vinyl cation


Calculated barrier 1.6 kcal/mole. Download IRC in xyz format

© Chem. Eur. J.