Experimental and Quantum Chemical Investigations of Binary Pnictido Stannate Zintl Anions and Ternary Intermetalloid Clusters

Felicitas Lips

ISBN 978-3-8325-3007-5
390 pages, year of publication: 2011
price: 98.00 €
Experimental and Quantum Chemical Investigations of Binary Pnictido Stannate Zintl Anions and Ternary Intermetalloid Clusters

In the last twenty years, the reactivity of homoatomic Zintl anions has been studied. For these investigations seven atom and nine atom Zintl anions have been reacted with transition metal complexes to yield ligand stabilized, "intermetalloid" or "alloy-like" cluster anions. Especially the latter two types of cluster anions exhibit complex, yet not entirely rationalized bonding situations and geometrical features.

In the first part of the present thesis, novel heteroatomic Zintl anions and a phenyl-ligated trimetallic cluster anion have been synthesized. In the second part, the reactivity of a known heteroatomic tetrahedral Zintl anion toward transition metal as well as lanthanide metal complexes was investigated, giving rise to a variety of ternary intermetalloid cluster anions. In all of the obtained clusters, the sort of main group element atoms that hold the majority of atoms in the cluster anions seem to determine the geometrical properties. The electronic situations within the cluster anions have been elucidated using quantum chemical investigations. These studies revealed that the cluster anions can be regarded as a Wade-type cluster anion, alloy-like molecular anions with complicated bonding situations or electron precise, fulleranetype Zintl anions. In the latter, magnetic properties are adjustable by the type of incorporated lanthanide ions.