Coupling Reactions of Functionalized Zintl Ions [E<sub>9</sub>Cd(C<sub>6</sub>H<sub>5</sub>)]<sup>3−</sup> (E = Sn, Pb) with Tributyltinhydride: Synthesis and Isolation of {Sn<sub>9</sub>CdSn[(CH<sub>2</sub>)<sub>3</sub>CH<sub>3</sub>]<sub>3</sub>}<sup>3−</sup>

Reaction of ethylenediamine solutions of K<sub>4</sub>E<sub>9</sub> (E = Sn, Pb) with diphenylcadmium yielded the Cd(C<sub>6</sub>H<sub>5</sub>)-functionalized Zintl ions, <i>closo</i>-[E<sub>9</sub>Cd(C<sub>6</sub>H<sub>5</sub>)]<sup>3−</sup> (E = Sn (<b>1</b>); Pb (<b>2</b>)). Solution reactivity studies of <b>1</b> with tributyltinhydride in pyridine revealed that the cluster is capable of undergoing a coupling reaction to yield the tributyltin-functionalized cluster, <i>closo</i>-{Sn<sub>9</sub>CdSn[(CH<sub>2</sub>)<sub>3</sub>CH<sub>3</sub>]<sub>3</sub>}<sup>3−</sup> (<b>3</b>). In-situ monitoring of this reaction by <sup>1</sup>H and <sup>13</sup>C{<sup>1</sup>H} NMR spectroscopy reveals the formation of the tributyltin functionalized cluster anion in addition to free benzene. Species <b>1</b>−<b>3</b> were characterized in the solid-state as [K(2,2,2-crypt)]<sup>+</sup> salts by single crystal X-ray diffraction and elemental analysis, while the presence of all three cluster anions in solution was confirmed by <sup>1</sup>H and <sup>13</sup>C{<sup>1</sup>H} NMR spectroscopy and electrospray mass-spectrometry.