Syntheses and Conformations of a Trinuclear Gold(I) System Based on a Triethinyl‐trisilacyclohexane Scaffold

Abstract

Trisilacyclohexanes and bissilylmethanes with acetylene units attached to silicon sites have been converted into tri‐ and dinuclear gold(I)phosphane complexes and characterized by NMR spectroscopy and X‐ray diffraction. The bissilylmethane‐based gold complexes were used as a test system to work out the synthetic routes before transferring them to the trisilacyclohexane scaffolds, because the latter are more difficult to access. The occurrence of aurophilic interactions (short Au···Au contacts) depends on the steric bulk of the phosphorus‐bonded alkyl and aryl groups. DFT studies show that dispersion effects play an important role in the ability to form intramolecular Au···Au interactions. QTAIM analyses show that a subtle change of the steric bulk of the phosphane groups alters the relative strength of the dispersion and aurophilic interactions. The combination of DFT studies and X‐ray diffraction experiments shows that the conformation of the trisilacyclohexane backbone is also phase dependent.