This thesis describes the reactivity of Zintl ions of groups 14 [E<sub>9</sub>]<sup>4–</sup> (E = Ge and Sn)and 15 [E'<sub>7</sub>]<sup>3–</sup> (E' = P and As) towards a number or transition, post-transition and main group reagents. The synthesis and characterisation of the resulting novel cluster anions is described herein. Coordination compounds of group 14 Zintl ions were synthesised when K<sub>4</sub>Ge<sub>9</sub> was reacted with Zn[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> to give the simple coordination compound [Ge<sub>9</sub>ZnN(SiMe<sub>3</sub>)<sub>2</sub>]<sup>3–</sup>. The heavier analogue K<sub>4</sub>Sn<sub>9</sub> reacts with the same metal precursor to give the paramagnetic species [Sn<sub>9</sub>ZnNSiMe<sub>3</sub>]<sup>3–</sup> where a trimethylsilyl group has been lost. K<sub>4</sub>Ge<sub>9</sub> reacts with [Ru(COD)(η<sup>3</sup>-CH<sub>2</sub>C(CH<sub>3</sub>)CH<sub>2</sub>)<sub>2</sub>] to form the paramagnetic endohedral compound [Ru@Ge<sub>12</sub>]<sup>3–</sup> and with [Co(PEt<sub>2</sub>Ph)<sub>2</sub>(mes)<sub>2</sub>] to form the prolate endohedral compound [Co<sub>2</sub>@Ge<sub>16</sub>]<sup>4–</sup>, which has two metal centres encapsulated inside the sixteen atom germanium cage. Regarding group 15 Zintl ion reactivity, the reactions between pyridine solutions of [HP<sub>7</sub>]<sup>2–</sup> and E[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> (E = Ge, Sn and Pb) have been found to yield coordination compounds of the type [P7E(N(SiMe3)2]2–. The germanium containing species [P<sub>7</sub>GeN(SiMe<sub>3</sub>)<sub>2</sub>]<sup>2–</sup> quickly decomposes at room temperature to give rise to the thermodynamic product [(P<sub>7</sub>)<sub>2</sub>Ge<sub>2</sub>N(SiMe<sub>3</sub>)<sub>2</sub>]<sup>3–</sup>, a process that involves the loss of an amide moiety. Activation products were also synthesised from the reaction of [E'<sub>7</sub>]<sup>3–</sup> with varying stoichiometries of VCp<sub>2</sub>. The reaction with 0.7 equivalents of VCp<sub>2</sub> yields the sandwich complexes [CpV(η<sup>5</sup>-E'<sub>5</sub>)]<sup>n–</sup> (E' = P: n = 1; E' = As, n = 1 and 2) whereas with 2.5 equivalents the products are the triple-decker sandwich complexes [(CpV)<sub>2</sub>(η<sup>x</sup>-E'<sub>x</sub>)]– (E' = P: x = 6; E' = As: x = 5).
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:668713 |
| Date | January 2015 |
| Creators | Espinoza Quintero, Gabriela |
| Contributors | Goicoechea, Jose M. |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:c5fe1201-5f9e-4417-95f2-e7eaeed80b64 |
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