Table 2.

NLMO contributions to the ¹³C isotropic nuclear shielding (σ_iso) in 3^a.

	σisoSR, SR-ZORA			σisoSO, SO-ZORA			ΔSO d
NLMOb	Lc	NLc	L + NL	L	NL	L + NL	L	NL	L + NL
σ(Ce-Caryl)	−103	2	−102	−156	2	−154	−52	0	−52
Σσ(Caryl-C1,2)	−106	−5	−110	−94	−5	−99	12	−1	11
1score (Caryl)	201	0	201	202	0	202	1	0	1
Σother	−26	11	−15	−25	11	−14	1	0	1
Σ(all of above)	−34	8	−26	−73	8	−65	−38	−1	−39e

^aDFT/PBEh-40 calculations. SR = scalar relativistic. SO = relativistic calculation including SOC. All shielding contributions are in ppm. The geometry orientation is such that the ¹³C corresponds to the origin of the cartesian axes and C–Ce bond aligns with the z-axis.

^bThe NLMOs are shown in Supplementary Fig. 41.

^cL and NL indicate contributions from the Lewis and non-Lewis parts of the NLMO.

^dDefined as σ_iso^SO − σ_iso^SR.

^eSOC effects of +1/−39 ppm on the reference/probe shielding cause the +40 ppm SOC change in the chemical shift quoted in the text.