Chemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ions
<p>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....
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| Médium: | Diplomová práce |
| Jazyk: | English |
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2015
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| Témata: |
| _version_ | 1826295727564783616 |
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| author | Espinoza Quintero, G |
| author2 | Goicoechea, J |
| author_facet | Goicoechea, J Espinoza Quintero, G |
| author_sort | Espinoza Quintero, G |
| collection | OXFORD |
| description | <p>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.</p> <p>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.</p> <p>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.</p> <p>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.</p> <p>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).</p> |
| first_indexed | 2024-03-07T04:05:30Z |
| format | Thesis |
| id | oxford-uuid:c5fe1201-5f9e-4417-95f2-e7eaeed80b64 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:05:30Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | oxford-uuid:c5fe1201-5f9e-4417-95f2-e7eaeed80b642022-03-27T06:35:05ZChemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ionsThesishttp://purl.org/coar/resource_type/c_db06uuid:c5fe1201-5f9e-4417-95f2-e7eaeed80b64Inorganic chemistryOrganometallic ChemistryChemistry & allied sciencesNMR spectroscopyChemical crystallographyEnglishOxford University Research Archive - Valet2015Espinoza Quintero, GGoicoechea, J<p>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.</p> <p>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.</p> <p>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.</p> <p>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.</p> <p>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).</p> |
| spellingShingle | Inorganic chemistry Organometallic Chemistry Chemistry & allied sciences NMR spectroscopy Chemical crystallography Espinoza Quintero, G Chemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ions |
| title | Chemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ions |
| title_full | Chemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ions |
| title_fullStr | Chemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ions |
| title_full_unstemmed | Chemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ions |
| title_short | Chemical reactivity of group 14 [E9]4– and 15 [E'7]3– Zintl ions |
| title_sort | chemical reactivity of group 14 e9 4 and 15 e 7 3 zintl ions |
| topic | Inorganic chemistry Organometallic Chemistry Chemistry & allied sciences NMR spectroscopy Chemical crystallography |
| work_keys_str_mv | AT espinozaquinterog chemicalreactivityofgroup14e94and15e73zintlions |