Solution reactivity studies of group 14 zintyl clusters towards organometallic reagents Zhou, Binbin Goicoechea, Jose Inorganic chemistry Crystallography Organometallic Chemistry metal clusters organometallic reagents Zintl anions <p>The group 14 Zintl clusters [E₉]⁴⁻ (E = Ge, Sn, Pb) have been reacted with organometallic reagents in solution in the presence of alkali metal cation sequestering agents. The synthesis, characterisation and reactivity studies of the resultant complexes are reported herein.</p><p>These negatively charged clusters reductively cleave one of the M–C bonds in the group 12 homoleptic organometallic reagents MR₂ (M = Zn, Cd; R = Ph, mes, ⁱPr) to yield η⁴-coordinated functionalised clusters closo-[E₉MR]³⁻. They can also activate both of the M–C bonds in Cd(mes)₂ to form metal-bridged dimers [Ge₉CdGe₉]⁶⁻ and [Pb₉CdCdPb₉]⁶⁻. Investigating the reactivity of the functionalised cluster [E₉CdPh]³⁻ (E = Sn, Pb) towards HSn(ⁿBu)₃ results in the synthesis of the novel closo-clusters [E₉CdSn(ⁿBu)₃]³⁻.</p><p>The reaction of K₄Ge₉ with the heteroleptic organometallic reagent Fe(COT)(CO)₃ yields the metalated cluster anion [Ge₈Fe(CO)₃]³⁻, in which the nuclearity of the Zintl anion is altered upon coordination of the [Fe(CO)₃] moiety. Two side products have also been isolated as [K(2,2,2-crypt)]⁺ salts of [Fe(η³-C₈H₈)(CO)₃]⁻ and [Fe₂(η³, η′³-C<sub<16</sub<H₁₆)(CO)₆]²⁻.</p><p>In the presence of highly reduced Zintl anions, all the M–C bonds in homoleptic mid-row transition metal organometallic reagents can also be cleaved. These ‘naked’ metal atoms have templated the formation of the endohedral clusters [Fe@Ge₁₀]³⁻, [Fe@Sn₁₀]³⁻ and [Mn@Pb₁₂]³⁻. These clusters adopt very different geometries and the electronic origin of their structures has been investigated in-depth by DFT calculations. Structural characterisation of some side products is also reported for: [E₉(mes)]³⁻ (E = Ge, Sn) and [Ge₉Mn(mes)]³⁻.</p> This thesis is not currently available via ORA. 2012 mixed material thesis born digital ora:6497 en urn:uuid:e5e50d36-579d-4d32-9de5-470bea1277d8