The metal-ligand spin distribution in the Mn and Ni complexes plays a crucial role in determining the contact chemical shifts. In these complexes with nondegenerate ground states and significant zero-field splitting within the 3d orbitals, comparing ZORA-PBE0 calculated spin densities in Fig. offers insight into this distribution. Pritchard et al. rationalized the reversal in the signs of the contact shifts between Fe(acac) and Cr(acac) complexes as resulting from possible ligand-to-metal (L-M) spin donations, enriching ligand atoms with opposite spins . Because in both the acac complexes the metal-to-ligand (M-L) spin transfer is mediated via the only available α(↑) spin in the 3d orbitals. Examining observed paramagnetic shifts in the Mn and Ni complexes (see Table ), the reversal of the 13 C and 1 H shifts signs in the N--C-CH 3 moiety is intriguing. The dominant spin transfer pathway observed in these complexes is M-L, as evidenced by the lack of significant β (↓) spin densities on the Mn ion in Fig. . This M-L spin transfer, mediated by the available α(↑) spin in Mn 3d orbitals, propagates through ligand atoms via combined spin delocalization and polarization mechanisms, leaving predominant α(↑) spin densities on ligand atoms. In the Ni complex, due to spatial differences between α and β 3d electrons in unrestricted calculations, M-L spin transfer can occur via both α(↑) and β (↓) spins, resulting in significant β (↓) spin densities on ligand atoms alongside α(↑) spin. Notably, significant α(↑) vs β (↓) spin densities on C=N carbon atoms (*C=N) in both complexes, as observed in Fig. , correlate with the sign alteration of 13 C chemical shifts (refer to Table ). Additionally, the downfield shift (-24 ppm) of CH 3 protons in the Ni complex, sharing spin of *C=N due to hyperconjugation, illustrates substantial M-L β (↓) spin transfer. Although the CH 3 proton signal in the Mn complex was not identified by Pavlov et al. , DFT results (Table ) suggest a highly upfield shift, likely obscured by a broad signal, consistent with highly upfield 13 C chemical shifts (807 ppm) of *C=N groups.