The recently observed nonintuitive pH dependence of methylene H-1 chemical shifts in cobalt(Ill) polyamine complexes upon deprotonation of coordinated aqua or (poly)alcohol coligands (J. Am. Chem. Soc. 2004, 126, 6728) was attributed to differential spin-orbit effects on the H-1 shifts transmitted over three bonds from the cobalt low-spin d(6) center. These remarkably large spin-orbit effects due to the comparably light Co center have now been examined closely by comparative computations for homologous Rh and Ir complexes, as well as by NMR titrations for a Rh complex. While larger spin-orbit effects (proportional to Z(2)) would have been expected for the heavier metal centers, the characteristic H-1 deshieldings upon deprotonation of [Rh(tren)(OH2)(2)](3+) [tren = tris(2-aminoethyl)-amine] turn out to be smaller than for the Co homologous Co complex. Systematic computational studies ranging from smaller models to the full complexes confirm these results and extend them to the Ir homologues. Closer analysis indicates that the spin-orbit shift contributions do not follow the expected 22 behavior but are modulated dramatically by increasing energy denominators in the perturbation expressions. This is related to the increasing ligand-field splitting from 3d to 4d to 5d system, leading to almost identical differential spin-orbit shifts for the Co and Rh complexes and to only moderately larger effects for the Ir complex (by a factor of about two). Moreover, the differential nonspin-orbit deprotonation shifts cancel the spin-orbit induced contributions largely in the Rh complex, leading to the experimentally observed inverted behavior. The full multidentate polyamine complexes studied experimentally exhibit different three- and four-bond Fermi-contact pathways for transmission of the spin-orbit H-1 shifts. The novel four-bond pathways have different conformational dependencies than the Karplus-like three-bond pathways established previously. Both types of contributions are of similar magnitude. The H-1 NMR deprotonation shift patterns of [Ir(tren)(OH2)(2)](3+) have been predicted computationally.