Journal article
Formation of a Silylated 1-Silaallene via an Intermediate 1-Chloro-1-silaallene



Publication Details
Authors:
Spirk, S.; Belaj, F.; Albering, J.; Pietschnig, R.
Publisher:
American Chemical SocietyDO - 10.1021/om100299w
Publication year:
2010
Journal:
Organometallics
Pages range:
2981-2986
Volume number:
29
Start page:
2981
End page:
2986
ISSN:
0276-7333

Abstract
Twofold conjugate addn. to 2,6-dimesitylphenyl-substituted dihaloalkynylsilane DmpSiCl2C≡CSiMe3 (Dmp = 2,6-dimesitylphenyl) yields silyl-substituted 1-silaallene Dmp(tBu)Si:C:C(tBu)SiMe3 rather than the isomeric silyne DmpSi≡CC(Me2)SiMe3. The dehalogenative intramol. carbometalation elimination using t-BuLi proceeds via stepwise dehalogenation involving intermediate 1-chloro-1-silaallene Dmp(Cl)Si:C:C(tBu)SiMe3. The authors' findings are backed by crystal structure analyses, spectroscopic data, and ab initio calcns. The completely dehalogenated 1-silaallene provides a silyl group at the silaallene core itself, which should allow further functionalization. [on SciFinder(R)]


Keywords
crystal structure silylated silaallene dihaloalkynylsilane prepn DFT frontier MO, ethynylchlorosilane reaction lithium terphenyl butyllithium, mol structure silylated silaallene dihaloalkynylsilane prepn DFT frontier MO, optimized mol structure silaallene silyne NMR GIAO shielding tensor


Authors/Editors

Last updated on 2019-25-07 at 15:26