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.
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Publisher: | American Chemical SocietyDO - 10.1021/om100299w
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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