TY - JOUR
T1 - Synthesis and reactivity of a novel oligosilyl anion
AU - Reinke, H.
AU - Krempner, Clemens
N1 - Funding Information:
We gratefully acknowledge the support of our work by the Fonds der Chemischen Industrie and we thank Prof. H. Oehme for his generous support.
PY - 2003/12/1
Y1 - 2003/12/1
N2 - A highly efficient route for the preparation of the sterically overcrowded oligosilyl anion TBTS-Li(THF)4 (3) {TBTS=Si[Si(SiMe3)2Me]3} in a large scale is reported. The reactions of HSiCl3 and SiCl 4 with 3 do not give coupling products, instead they produce TBTS-H and TBTS-Cl, probably as a result of steric interactions. On the contrary, PhSiF3 and SiF4 can be reacted with 3 to give TBTS-SiF3 (5) and TBTS-SiF2Ph (6), respectively, in excellent yields. The X-ray analysis revealed 6 to be a sterically overcrowded molecule, in which the SiF2Ph group is strongly shielded by the TBTS substituent. Despite the extensive space demand of the TBTS group, 5 and 6 can be transformed into TBTS-SiH3 (7) and TBTS-SiH2Ph (8) by treatment with LiAlH4. The controlled hydrolysis of 5 leads to the selective formation of TBTS-SiF2OH (9), the first isolated difluorosilanol, which is stable towards condensation.
AB - A highly efficient route for the preparation of the sterically overcrowded oligosilyl anion TBTS-Li(THF)4 (3) {TBTS=Si[Si(SiMe3)2Me]3} in a large scale is reported. The reactions of HSiCl3 and SiCl 4 with 3 do not give coupling products, instead they produce TBTS-H and TBTS-Cl, probably as a result of steric interactions. On the contrary, PhSiF3 and SiF4 can be reacted with 3 to give TBTS-SiF3 (5) and TBTS-SiF2Ph (6), respectively, in excellent yields. The X-ray analysis revealed 6 to be a sterically overcrowded molecule, in which the SiF2Ph group is strongly shielded by the TBTS substituent. Despite the extensive space demand of the TBTS group, 5 and 6 can be transformed into TBTS-SiH3 (7) and TBTS-SiH2Ph (8) by treatment with LiAlH4. The controlled hydrolysis of 5 leads to the selective formation of TBTS-SiF2OH (9), the first isolated difluorosilanol, which is stable towards condensation.
KW - Fluorosilanes
KW - Silanes
KW - Silicon
KW - Silyl anions
UR - http://www.scopus.com/inward/record.url?scp=0142024994&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(03)00625-9
DO - 10.1016/S0022-328X(03)00625-9
M3 - Article
AN - SCOPUS:0142024994
SN - 0022-328X
VL - 686
SP - 158
EP - 163
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -