ic6b02727_si_002.pdf (688.04 kB)
Donor–Acceptor Stabilized Tetra(silanimine)
journal contribution
posted on 2017-01-17, 19:36 authored by Yu-Liang Shan, Bi-Xiang Leong, Yongxin Li, Rakesh Ganguly, Cheuk-Wai SoThe
synthesis of an oligo(silanimine) is described. The reaction of the
amidinato silylene [LSiN(SiMe3)2] (1, L = PhC(NtBu)2) with SiI4 in toluene afforded a mixture of the silanimine [LSi(I)NSiI3] (2), SiMe3I, and Si2I6. The mechanistic studies showed that 1 reacts
with SiI4 to form the silyl ionic intermediate “{LSi(I)N(SiMe3)2}+{SiI3}−”, which then eliminates SiMe3I and “SiI2” to form the silanimine intermediate “LSi(I)NSiMe3”. It further undergoes a substitution with another
molecule of SiI4 to form a mixture of 2 and
SiMe3I. In addition, “SiI2” undergoes
an oxidative addition with SiI4 to form Si2I6. Subsequently, compound 2 reacted with [LiN(SiMe3)Ar] to form the silanimine [LSi(I)NSiI2N(SiMe3)Ar] (6, Ar = 2,6-iPr2C6H3), which was then treated with KC8 to give the donor–acceptor stabilized tetra(silanimine) [LSiN(SiMe3)SiNAr]2 (7). It comprises four formal
silanimine “>SiN-” units, which are linked
together. Compounds 2, 6, and 7 were characterized by NMR spectroscopy and X-ray crystallography.