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

We report the synthesis of the U(iii) bis(cyclopentadienyl) hypersilanide complex [U(Cp′′)(2){Si(SiMe(3))(3)}] (Cp′′ = {C(5)H(3)(SiMe(3))(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(SiMe(3))(3)}] (M = Ti, Zr, La, Ce, Nd, U) series the unique anisotropy axis is conserved tangential to [Image: see text]; 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 5f(3) U(iii) vs. 4f(3) 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′′.