Calculated and experimental shift parameters for the proximal (denoted by p) and distal (denoted by d) –SiMe₃ group of Yb^III(CH(SiMe₃)₂)₃ in the Haeberlen convention after a three-site fast exchange averaging of the shielding tensors. The shielding tensor is computed according to 2 where the magnetic susceptibility tensor has been computed with the SO-CASPT2 method and the hyperfine tensors are either from the SO-CASSCF or DFT(PBE0) methods. Long-range contributions has been accounted using the semi-classical point dipolar equation according to eqn (S10).

Method		29Si		13C		1H
		p	d	p	d	p	d
	δ orb	−10.7	−9.2	2.8	4.6	0.2	0.4
	δ LR	16.9	16.5	28.5	9.5	15.6	27.6
SO-CASPT2/CASSCF	δ SD	−67.4	−9.6	−4.4	0.5	7.4	2.1
	δ PSO	−201.0	−29.2	−15.9	1.7	21.4	6.6
	δ FC	3.0	7.6	2.4	0.5	0.2	0.0
	δ total	−259.2	−23.9	13.4	16.8	44.8	36.7
	Δδ	−493.2	−19.3	−41.4	−28.4	10.2	21.8
SO-CASPT2/PBE0	δ SD	−61.2	−10.2	−1.1	−0.4	6.3	1.9
	δ PSO	−78.4	−10.3	−8.6	1.0	7.4	2.4
	δ FC	−24.4	−77.4	67.7	14.7	3.0	0.4
	δ total	−157.8	−90.6	89.3	29.4	32.5	32.7
	Δδ	−321.8	−122.0	−256.6	−51.0	25.1	18.3
Exp	δ	−220 ± 20	−30 ± 30	40 ± 20	−20 ± 20	30 ± 20	−20 ± 20
	Δδ	−542 ± 3	409 ± 3	−183 ± 4	140[+30, −270]	153 ± 1	−56 ± 1