RESUMO
During the last three decades, silicon-bridged [1]ferrocenophanes have been developed into an important class of monomers with the resulting polymers being the subject of hundreds of publications. For unknown reasons, not a single example of a silicon-bridged [1]ruthenocenophane is described in the literature. We set out to address this mystery and could synthesize the first sila[1]ruthenocenophanes. Their molecular structures as well as their heat release in the melt, render them as highly strained sandwich compounds that are polymerizable. Why did it take so long to prepare the first sila[1]ruthenocenophanes? This question is addressed by a detailed analysis of the kinetics of the salt-metathesis approach, which reveals a striking difference between ferrocene and ruthenocene.
RESUMO
A set of four planar-chiral sila[1]ferrocenophanes equipped with a benzyl group in the α-position, either on one or both Cp rings, and substituted on the bridging silicon atom, either by methyl or phenyl groups, were prepared. While NMR, UV/Vis, and DSC measurements did not show anything uncommon, single crystal X-ray analyses revealed unexpectedly large variations of the dihedral angles between both Cp rings (α tilt angle). While DFT calculations predicted α between 19.6 and 20.8°, measured values were found between 16.6(2) and 21.45(14)°. However, experimentally determined conformers differ significantly from those calculated for the gas phase. For the sila[1]ferrocenophane with the largest mismatch between the experimental and predicted α angle, it was shown that the orientation of benzyl groups have a significant influence on the ring-tilted structure. Packing of molecules in the crystal lattice forces benzyl groups into unusual orientations, resulting in a significantly reduced α angle through steric repulsions.