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Donor–Acceptor Stabilized Tetra(silanimine)
No full textThe
synthesis of an oligo(silanimine) is described. The reaction of the
amidinato silylene [LSiN(SiMe<sub>3</sub>)<sub>2</sub>] (<b>1</b>, L = PhC(N<i>t</i>Bu)<sub>2</sub>) with SiI<sub>4</sub> in toluene afforded a mixture of the silanimine [LSi(I)NSiI<sub>3</sub>] (<b>2</b>), SiMe<sub>3</sub>I, and Si<sub>2</sub>I<sub>6</sub>. The mechanistic studies showed that <b>1</b> reacts
with SiI<sub>4</sub> to form the silyl ionic intermediate “{LSi(I)N(SiMe<sub>3</sub>)<sub>2</sub>}<sup>+</sup>{SiI<sub>3</sub>}<sup>−</sup>”, which then eliminates SiMe<sub>3</sub>I and “SiI<sub>2</sub>” to form the silanimine intermediate “LSi(I)NSiMe<sub>3</sub>”. It further undergoes a substitution with another
molecule of SiI<sub>4</sub> to form a mixture of <b>2</b> and
SiMe<sub>3</sub>I. In addition, “SiI<sub>2</sub>” undergoes
an oxidative addition with SiI<sub>4</sub> to form Si<sub>2</sub>I<sub>6</sub>. Subsequently, compound <b>2</b> reacted with [LiN(SiMe<sub>3</sub>)Ar] to form the silanimine [LSi(I)NSiI<sub>2</sub>N(SiMe<sub>3</sub>)Ar] (<b>6</b>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>), which was then treated with KC<sub>8</sub> to give the donor–acceptor stabilized tetra(silanimine) [LSiN(SiMe<sub>3</sub>)SiNAr]<sub>2</sub> (<b>7</b>). It comprises four formal
silanimine “>SiN-” units, which are linked
together. Compounds <b>2</b>, <b>6</b>, and <b>7</b> were characterized by NMR spectroscopy and X-ray crystallography
