The reactivity of group 15 Zintl ions, E<sub>7</sub><sup>3–</sup> (E = P, As), towards a number of transition and post-transition metal reagents has been studied. The synthesis and characterisation of the resulting novel cluster anions are described herein. The reactions of E<sub>7</sub><sup>3–</sup> with [Cu<sub>5</sub>(mes)<sub>5</sub>], MPh<sub>2</sub> (M = Zn, Cd) and InPh<sub>3</sub> yielded the Cu–Cu bridged species [Cu<sub>2</sub>(E<sub>7</sub>)<sub>2</sub>]<sup>4–</sup> (E = P, As), the group 12 bridged cluster anions [M(E<sub>7</sub>)<sub>2</sub>]<sup>4–</sup> (M = Zn: E = P, As; M= Cd: E = P), and the In-functionalised Zintl ions [E<sub>7</sub>InPh<sub>2<sub>]<sup>2–</sup>, respectively. P<sub>7</sub><sup>3–</sup> and As<sub>7</sub><sup>3–</sup> have been found to react with a number of metal salts, namely [M(nbe)<sub>3</sub>][SbF<sub>6</sub>] and MCl (M = Ag, Au), InCl<sub>3</sub>, TlCl and MI<sub>2</sub> (M = Sn, Pb). These reactions formed the Ag–Ag and Au–Au bridged complexes [M<sub>2</sub>(HP<sub>7</sub>)<sub>2</sub>]<sup>2–</sup> (M = Ag, Au), the In-bridged species [In(E<sub>7</sub>)<sub>2</sub>]<sup>3–</sup> (E = P, As), the Tl-derivatised Zintl ions [TlE<sub>7</sub>]<sup>2–</sup> (E = P, As), and the sixteen vertex cluster anions [ME<sub>15</sub>]<sup>3–</sup> (M = Sn, Pb; E = P, As). The reactivity of P<sub>7</sub><sup>3–</sup> towards a series of group 8 compounds has also been studied. The reactions of P<sub>7</sub><sup>3–</sup> with FeCl<sub>2</sub> and [Ru(PPh<sub>3</sub>)<sub>3</sub>Cl<sub>2</sub>] produced [M(HP<sub>7</sub>)<sub>2</sub>]<sup>2-</sup> (M = Fe, Ru). NMR studies showed that these species can be deprotonated to form [M(P<sub>7</sub>)<sub>2</sub>]<sup>4–</sup> (M = Fe, Ru). These Fe and Ru complexes are isoelectronic with ferrocene. In addition, P<sub>7</sub><sup>3–</sup> 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 [(C<sub>4</sub>H<sub>7</sub>)P<sub>7</sub>Ru(COD)]<sup>2–</sup>. Both P<sub>7</sub><sup>3–</sup> and As<sub>7</sub><sup>3–</sup> undergo transition metal mediated activation reactions in the presence of [Co(PEt<sub>2</sub>Ph<sub>2</sub>)(mes)<sub>2</sub>], yielding [Co(η<sup>5</sup>-P<sub>5</sub>){η<sup>2</sup>-HP<sub>2</sub>(mes)}]<sup>2–</sup> and [Co([η<sup>3</sup>-As<sub>3</sub>){η<sup>4</sup>-As<sub>4</sub>(mes)<sub>2</sub>}]<sup>2–</sup>, respectively.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:588461 |
| Date | January 2013 |
| Creators | Knapp, Caroline Mary |
| 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:0196fc28-2915-45f4-878d-12a6a1f01129 |
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