ISSN:
0009-2940
Keywords:
Silanes, aminofluoro-
;
Insertion
;
Isomerisation
;
Cycloaddition
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Insertion, Isomerization, and Cycloaddition Reactions of Lithiated Aminofluorosilanes*The lithium derivative 2 of (di-tert-butylfluorosilyl)(fluorodi-isopropylsilyl)amine (1) reacts with benzoyl chloride to form the imines 3I and 3II in an insertion reaction. LiF elimination from 2 leads to the cyclodisilazane [(CMe3)2SiFN - Si(CHMe2)2]2 (4). The fluorine atom of the SiF(CHMe2) group in 1 can be substituted by means of LiOSiMe3 to yield 5. The lithium derivative of 5 (6) is a dimer with very short Li - F distances. The lithium derivative 6 reacts with benzaldehyde in a [2 + 2] cycloaddition to give an (SiNCO) four-membered ring compound (7), which thermally decomposes to yield the imine 8 and a cyclosiloxane, A fluorine/chlorine exchange is observed when Me3SiCl is added to the lithium derivative 6. The resulting unstable lithium derivative of an aminochlorosilane eliminates LiCl to form the cylcodisilazane 9. According to a crystal structure determination the formation of 9 involves isomerization of the intermediate iminosilane followed by dimerization.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250405
