Coordination chemistry of main group cyclopentadienyl compounds

Abstract

Der erste Teil dieser Arbeit beschäftigt sich mit Carbenaddukten von Gruppe 14 Metallocenen und verwandten Zinn(II) Halbsandwichkomplexen. Diese Verbindungen sind die ersten ihrer Art, was einen wichtigen Beitrag zur Klasse der Carbenkomplexe tetrylenartiger Verbindungen darstellt. Im zweiten Teil wurden phosphanylsubstituierte Metallocene und abgeleitete Koordinationsverbindungen des Magnesiums, Antimons und der Gruppe 14 Elemente, Germanium, Zinn und Blei, untersucht. Diese Verbindungen zeigen einen Lewis amphiphilen Charakter.

The first part of this thesis deals with complexes of N-heterocyclic carbenes with group 14 metallocenes as well as with complexes of a cyclic (alkyl)(amino)carbene with related tin(II) halfsandwich complexes. The bonding nature in these complexes was examined using DFT calculations, which revealed that attractive dispersion force interactions play a substantial role. These complexes are the first of their kind representing an important contribution to the class of carbene complexes of tetrylene-type compounds. In the second part of this thesis, phosphanyl substituted metallocenes and derived coordi-nation compounds of magnesium, antimony and the group 14 elements, germanium, tin and lead, were investigated. These compounds exhibit Lewis amphiphilic character due to the Lewis acidic central atoms and the Lewis basic phosphorus atoms. The phosphanyl substi-tuted magnesocenes, which are the first donor-functionalized magnesocenes, could be used both to activate small molecules and as ligands for transition metal fragments. The coordi-nation chemistry of the corresponding group 14 metallocenes, which were obtained by transmetalation of the magnesocenes, was studied extensively towards main group and transition metal fragments, whereby significant structural differences to the related phospha-nyl substituted ferrocenes were found.