Novel 10- and 20- membered tin- and silicon-containing rings: synthesis, complexation behavior and conversion into a lewis acidic polymer
journal contribution
posted on 2003-01-01, 00:00 authored by M Schulte, G Gabriele, M Schurmann, K Jurkschat, Andrew DuthieAndrew Duthie, Dainis DakternieksReaction of the dimethylsilylmethyl-substituted tetraorganotin derivative CH<sub>2</sub>[CH<sub>2</sub>Sn(Ph<sub>2</sub>)CH<sub>2</sub>Si(H)Me<sub>2</sub>]<sub>2</sub> (<b>1</b>) and CH<sub>2</sub>[CH<sub>2</sub>Sn(Ph<sub>2</sub>)CH<sub>2</sub>Si(<i>i</i>-PrO)Me<sub>2</sub>]<sub>2</sub> (<b>3</b>), respectively, with mercuric chloride afforded the novel silicon- and tin-containing 10- and 20-membered rings <i>cyclo</i>-CH<sub>2</sub>[CH<sub>2</sub>Sn(Cl<sub>2</sub>)CH<sub>2</sub>Si(Me<sub>2</sub>)]<sub>2</sub>O (<b>4</b>) and <i>cyclo</i>-CH<sub>2</sub>[CH<sub>2</sub>Sn(Cl<sub>2</sub>)CH<sub>2</sub>Si(Me<sub>2</sub>)OSi(Me<sub>2</sub>)CH<sub>2</sub>Sn(Cl<sub>2</sub>)CH<sub>2</sub>]<sub>2</sub>CH<sub>2</sub> (<b>5</b>). Both compounds <b>4</b> and <b>5</b> can be converted into the soluble Lewis acidic polymer poly-[Si(Me<sub>2</sub>)CH<sub>2</sub>Sn(Cl<sub>2</sub>)(CH<sub>2</sub>)<sub>3</sub>Sn(Cl<sub>2</sub>)CH<sub>2</sub>Si(Me<sub>2</sub>)O] (<b>8</b>). <sup>119</sup>Sn NMR studies indicate that <b>4</b> acts as a bidentate Lewis acid toward chloride ions, exclusively forming the 1:1 complex [<i>cyclo</i>-CH<sub>2</sub>[CH<sub>2</sub>Sn(Cl<sub>2</sub>)CH<sub>2</sub>Si(Me<sub>2</sub>)]<sub>2</sub>O·Cl]-[(Ph<sub>3</sub>P)<sub>2</sub>N]<sup>+</sup> (<b>7</b>). The molecular structures as determined by single-crystal X-ray diffraction analysis of <b>4</b> and <b>7</b> are reported. <br>
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