Electronic structure comparisons of isostructural early d- and f-block metal(iii) bis(cyclopentadienyl) silanide complexes

Abstract

We report the synthesis of the U(III) bis(cyclopentadienyl) hypersilanide complex [U(Cp′′)₂{Si(SiMe₃)₃}] (Cp′′ = {C₅H₃(SiMe₃)₂-1,3}), together with isostructural lanthanide and group 4 M(III) homologues, in order to meaningfully compare metal-silicon bonding between early d- and f-block metals. All complexes were characterised by a combination of NMR, EPR, UV-vis-NIR and ATR-IR spectroscopies, single crystal X-ray diffraction, SQUID magnetometry, elemental analysis and ab initio calculations. We find that for the [M(Cp′′)₂{Si(SiMe₃)₃}] (M = Ti, Zr, La, Ce, Nd, U) series the unique anisotropy axis is conserved tangential to ; this is governed by the hypersilanide ligand for the d-block complexes to give easy plane anisotropy, whereas the easy axis is fixed by the two Cp′′ ligands in f-block congeners. This divergence is attributed to hypersilanide acting as a strong σ-donor and weak π-acceptor with the d-block metals, whilst f-block metals show predominantly electrostatic bonding with weaker π-components. We make qualitative comparisons on the strength of covalency to derive the ordering Zr > Ti ≫ U > Nd ≈ Ce ≈ La in these complexes, using a combination of analytical techniques. The greater covalency of 5f³ U(III) vs. 4f³ Nd(III) is found by comparison of their EPR and electronic absorption spectra and magnetic measurements, with calculations indicating that uranium 5f orbitals have weak π-bonding interactions with both the silanide and Cp′′ ligands, in addition to weak δ-antibonding with Cp′′.