"Journal of Chemical Theory and Computation" . . . . . . "Relativistic effects play an essential role in understanding the nuclear magnetic resonance (NMR) chemical shifts in heavy-atom compounds. Particularly interesting from the chemical point of view are the relativistic effects due to heavy atom (HA) on the NMR chemical shifts of the nearby light atoms (LA), referred to as the HALA effects. The effect of Spin-Orbit (SO) interaction originating from HA on the nuclear magnetic shielding at a neighboring LA, sigmaSO, is explored here in detail for a series of d6 complexes of iridium. Unlike the previous findings, the trends in sigmaSO observed in this study can be fully explained neither in terms of the s-character of the HA-LA bonding nor by trends in the energy differences between occupied and virtual molecular orbitals (MOs). Rather, the sigmaSO contribution to the total NMR shielding is found to be modulated by the d-orbital participation of the heavy atom (Ir) in the occupied and virtual spin-orbit active MOs, i.e."@en . . . . . . "http://dx.doi.org/10.1021/ct400726y" . "4" . "RIV/00216224:14740/14:00073495" . . "10" . "NMR shielding; spin-orbit coupling; d-orbitals; mechanism; transition-metal complex; iridium; EPR; g-tensor; A-tensor"@en . "14740" . "1549-9618" . . . . . . . "RIV/00216224:14740/14:00073495!RIV15-MSM-14740___" . "28134" . "Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR"@en . "Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR"@en . "Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR" . . . "Munzarov\u00E1, Mark\u00E9ta" . "Straka, Michal" . . . "4"^^ . . "US - Spojen\u00E9 st\u00E1ty americk\u00E9" . "4"^^ . "I, P(ED1.1.00/02.0068), P(GAP206/12/0539)" . "Marek, Radek" . . "000334571900013" . . "V\u00EDcha, Jan" . "Relativistic effects play an essential role in understanding the nuclear magnetic resonance (NMR) chemical shifts in heavy-atom compounds. Particularly interesting from the chemical point of view are the relativistic effects due to heavy atom (HA) on the NMR chemical shifts of the nearby light atoms (LA), referred to as the HALA effects. The effect of Spin-Orbit (SO) interaction originating from HA on the nuclear magnetic shielding at a neighboring LA, sigmaSO, is explored here in detail for a series of d6 complexes of iridium. Unlike the previous findings, the trends in sigmaSO observed in this study can be fully explained neither in terms of the s-character of the HA-LA bonding nor by trends in the energy differences between occupied and virtual molecular orbitals (MOs). Rather, the sigmaSO contribution to the total NMR shielding is found to be modulated by the d-orbital participation of the heavy atom (Ir) in the occupied and virtual spin-orbit active MOs, i.e." . "[3BD76F2121C9]" . "11"^^ . . . "Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR" . "10.1021/ct400726y" .