Transient Silenes as Versatile Synthons – The Reaction of Dichloromethyl-tris(trimethylsilyl)silane with Organolithium Reagents
✍ Scribed by Kathleen Schmohl; Thoralf Gross; Helmut Reinke; Hartmut Oehme
- Publisher
- John Wiley and Sons
- Year
- 2000
- Tongue
- German
- Weight
- 108 KB
- Volume
- 626
- Category
- Article
- ISSN
- 0372-7874
No coin nor oath required. For personal study only.
✦ Synopsis
Treatment of dichloromethyl-tris(trimethylsilyl)silane (Me 3 Si) 3 Si±CHCl 2 (1), prepared by the reaction of tris(trimethylsilyl)silane with chloroform in presence of potassium tertbutoxide, with organolithium reagents (molar ratio 1 : 3) affords the bis(trimethylsilyl)methyl-disilanes Me 3 SiSiR 2 ±CH(SiMe 3 ) 2 (12 a±d) (a: R = Me, b: R = n-Bu, c: R = Ph, d: R = Mes). The formation of 12 a±d is discussed as proceeding through an exceptional series of isomerization and addition reactions involving intermediate silyl substituted carbenoids and transient silenes. The carbenoid (Me 3 Si) 2 PhSi±C(SiMe 3 )LiCl (8 c) is moderately stable at low temperature and was trapped with water to give (Me 3 Si) 2 PhSi±CH(SiMe 3 )Cl (9 c) and with chlorotrimethylsilane affording (Me 3 Si) 2 PhSi±CCl(SiMe 3 ) 2 (7 c). For 12 d an X-ray crystal structure analysis was performed, which characterizes the compound as a highly congested silane with bond parameters significantly deviating from standard values.