Sterically demanding N,N′,N′-substituted 1,2-ethanediamine ligands have been prepared from commercially available starting materials by applying a facile one-step procedure. These ligands offer advantages compared to known systems: a suppressed delocalization due to the saturated backbone inhibits a noninnocent behaviour and the low symmetry of the related metal complexes makes them potential candidates for asymmetric catalysis. The ligands are readily transformed into the corresponding lithium derivatives 4, which in turn act as starting materials to access the corresponding aluminium and gallium dichlorides 5 and 6, respectively. In addition, deprotonation by Al(CH3)3 gives rise to the related dimethylalane 7. All main-group element compounds have been studied by means of single X-ray crystallography and spectroscopic methods.

A facile and efficient one-pot strategy for the preparation of 1,2,3-tri- and 1,1,2,3-tetrasubstituted bis(guanidine)s by starting from from readily available bis(thiourea)s has been successfully developed. The reaction provides products that contain a range of terminal and bridging groups. After a simple workup procedure, the products were obtained in analytically pure and in good to excellent yields.

Using bis(β-diketiminate) ligands we were able to synthesize unprecedented indium and thallium biscarbenoids. For indium, a novel four-membered metallacycle is derived from intra- and intermolecular In–In interactions in the solid state, while for thallium only an intramolecular Tl2-pseudo-dimer is obtained. Computational studies revealed that the solid-state structures benefit significantly from dispersion stabilization.

Using bis(β-diketiminate) ligands we were able to synthesize unprecedented indium and thallium biscarbenoids. For indium, a novel four-membered metallacycle is derived from intra- and intermolecular In–In interactions in the solid state, while for thallium only an intramolecular Tl2-pseudo-dimer is obtained. Computational studies revealed that the solid-state structures benefit significantly from dispersion stabilization.