Th e Study of Labile Silylene Reactions Using Matrix IR Spectroscopy

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Using matrix IR spectroscopy, complexes of SiCl2 with CO2 and CO were stabilized in argon matrices at ~10 K and spectroscopically characterized. Complex Cl2Si•CO2 is the first experimentally detected complex of any silylenes with CO2. It is found that under matrix conditions, it exists in a photochemical equilibrium with the isomeric complex Cl2Si=O•CO, with the equilibrium being strongly shifted towards Cl2Si•CO2. The detected complex Cl2Si•CO with the coordination of the silylene to the C atom is the first unclassical complex of silylenes. The first complex with the silylene coordination to the O atom of CO, Cl2Si•OC, was also detected. Using matrix IR spectroscopy, photochemical transformations of one of the simplest labile silylenes, dimethoxysilylene, Si(OMe)2, were studied, all its conformers were revealed. It was confirmed that the only product of its photoisomerisation is labile methylmethoxysilanone, Me(MeO)Si=O. Potential energy surfaces of the studied systems were explored using quantum chemical calculations.

Sobre autores

Sergey Boganov

N.D. Zelinsky Institute of Organic Chemistry, RAS

Autor responsável pela correspondência
Email: bog@ioc.ac.ru
Rússia, 47 Leninsky Ave., Moscow, 119991, Russia

Vladimir Promyslov

N.D. Zelinsky Institute of Organic Chemistry, RAS

Email: vladimir-promyslov@yandex.ru
Rússia, 47 Leninsky Ave., Moscow, 119991, Russia

Irina Krylova

N.D. Zelinsky Institute of Organic Chemistry, RAS

Email: kiv@ioc.ac.ru
Rússia, 47 Leninsky Ave., Moscow, 119991, Russia

Pavel Shangin

N.D. Zelinsky Institute of Organic Chemistry, RAS

Email: shangin@ioc.ac.ru
Rússia, 47 Leninsky Ave., Moscow, 119991, Russia

Mikhail Syroeshkin

N.D. Zelinsky Institute of Organic Chemistry, RAS

Email: syroeshkin@ioc.ac.ru
Rússia, 47 Leninsky Ave., Moscow, 119991, Russia

Mikhail Egorov

N.D. Zelinsky Institute of Organic Chemistry, RAS

Email: mpe@ioc.ac.ru

Academician, Director

Rússia, 47 Leninsky Ave., Moscow, 119991, Russia

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Declaração de direitos autorais © Boganov S.E., Promyslov V.M., Krylova I.V., Shangin P.G., Syroeshkin M.A., Egorov M.P., 2024

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