Based on previous observations of similar isotropic and dipolar parts of hyperfine coupling tensors for the S = 1/2 Ti(III) alkyl complexes, the observed 1 H hyperfine couplings could be assigned to the hydrogen atoms that are close in space to the Yb(III) centre, such as α-H atoms of CH(SiMe 3 ) 2 ligands. The positions of the α-H atoms within the structure of Yb[CH(SiMe 3 ) 2 ] 3 were further refined using quantum chemical computations (vide infra).