ISSN:
1434-1948
Keywords:
Silicon
;
Silanes, sterically congested
;
Tris(trimethylsilyl)silanes
;
(Chloromethylene)ammonium chlorides
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Tris(trimethylsilyl)silyllithium (1) reacts with dialkyl(chloromethylene)ammonium chlorides (molar ratio 2:1) to give the (dialkylamino)bis(hypersilyl)methanes [(Me3Si)3Si]2CHNR2 (5a-c; a: R = Me, b: R = Et, c: R2 = [CH2]5). Due to the extreme bulkiness of the hemispherical (Me3Si)3Si substituents, the structures of these geminal bis(hypersilyl) derivatives are characterized by tremendous distortions of their molecular skeletons. This was confirmed by X-ray structural analyses of 5a and 5c, which revealed considerable elongations of the central Si-C bonds (5a: 2.01 and 1.95 Å; 5c: 1.99 and 1.97 Å) and an extreme widening of the Si-C-Si angles at the central sp3-carbon atoms (5a: 132.6°; 5c: 128.7°). By concentrated sulfuric acid, 5a is converted to give, after hydrolysis, the silanol (Me3Si)2Si(OH)-CH2Si(SiMe3)3 (13). The formation of 13 is discussed as proceeding through the transient silene (Me3Si)2Si=CHSi(SiMe3)3 (11), generated by a formal (dimethylamino)trimethylsilane elimination from 5a according to an acid-induced sila Peterson mechanism.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
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