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Title: Solution reactivity studies of group 15 Zintl ions
Author: Knapp, Caroline Mary
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2013
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The reactivity of group 15 Zintl ions, E73– (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 E73– with [Cu5(mes)5], MPh2 (M = Zn, Cd) and InPh3 yielded the Cu–Cu bridged species [Cu2(E7)2]4– (E = P, As), the group 12 bridged cluster anions [M(E7)2]4– (M = Zn: E = P, As; M= Cd: E = P), and the In-functionalised Zintl ions [E7InPh2]2–, respectively. P73– and As73– have been found to react with a number of metal salts, namely [M(nbe)3][SbF6] and MCl (M = Ag, Au), InCl3, TlCl and MI2 (M = Sn, Pb). These reactions formed the Ag–Ag and Au–Au bridged complexes [M2(HP7)2]2– (M = Ag, Au), the In-bridged species [In(E7)2]3– (E = P, As), the Tl-derivatised Zintl ions [TlE7]2– (E = P, As), and the sixteen vertex cluster anions [ME15]3– (M = Sn, Pb; E = P, As). The reactivity of P73– towards a series of group 8 compounds has also been studied. The reactions of P73– with FeCl2 and [Ru(PPh3)3Cl2] produced [M(HP7)2]2- (M = Fe, Ru). NMR studies showed that these species can be deprotonated to form [M(P7)2]4– (M = Fe, Ru). These Fe and Ru complexes are isoelectronic with ferrocene. In addition, P73– reacts with [Ru(COD)(η3-CH2C(CH3)CH2)2] to form [(C4H7)P7Ru(COD)]2–. Both P73– and As73– undergo transition metal mediated activation reactions in the presence of [Co(PEt2Ph2)(mes)2], yielding [Co(η5-P5){η2-HP2(mes)}]2– and [Co([η3-As3){η4-As4(mes)2}]2–, respectively.
Supervisor: Goicoechea, Jose M. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Co-ordination chemistry ; Inorganic chemistry ; Organometallic Chemistry ; Zintl ions ; clusters