Reaction of (bromodifluoromethyl)trimethylsilane with HMPA: Structural studies

Reaction of (bromodifluoromethyl)trimethylsilane with HMPA: Structural studies Full article

Journal

Journal of Fluorine Chemistry
ISSN: 1873-3328 , E-ISSN: 0022-1139

Output data

Year: 2021, Volume: 250, Article number : 109881, Pages count : DOI: 10.1016/j.jfluchem.2021.109881

Authors

Supranovich Vyacheslav I. ¹ , Volodin Alexander D. ^2,3 , Korlyukov Alexander A. ^2,4 , Hu Jinbo ⁵ , Dilman Alexander D. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, Moscow 119991, Russian Federation
2	A. N. Nesmeyanov Institute of Organoelement Compounds, Vavilova str. 28, Moscow 119991, Russian Federation
3	D. Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow 125047, Russian Federation
4	Pirogov Russian National Research Medical University, Ostrovityanova st. 1, Moscow 117997, Russian Federation
5	Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China

The crystal structure of a low melting difluorinated silicon reagent (bromodifluoromethyl)trimethylsilane is described. Hexamethylphosphoramide (HMPA) serves as an efficient Lewis basic activator to decompose the silicon reagent to generate difluorocarbene along with the formation of silyl-capped HMPA cation. The bromide salt with Me3Si-HMPAcation was also obtained by interaction of bromotrimethylsilane with HMPA and was characterized by X-ray analysis. Interaction of silanes with HMPA was evaluated by quantum chemical calculations, which demonstrated that the Lewis base provides a significant decrease of the transition state energy for the generation of difluorocarbene by an attack at the silicon atom.

Supranovich V.I. , Volodin A.D. , Korlyukov A.A. , Hu J. , Dilman A.D.
Reaction of (bromodifluoromethyl)trimethylsilane with HMPA: Structural studies
Journal of Fluorine Chemistry. 2021. V.250. 109881 . DOI: 10.1016/j.jfluchem.2021.109881 WOS Scopus OpenAlex

Web of science:	WOS:000695814300010
Scopus:	2-s2.0-85114027281
OpenAlex:	W3195333231

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