VÍCHA, Jan, Michal STRAKA, Markéta MUNZAROVÁ and Radek MAREK. Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR. Journal of Chemical Theory and Computation. Washington: American Chemical Society, 2014, vol. 10, No 4, p. 1489-1499. ISSN 1549-9618. doi:10.1021/ct400726y.
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Basic information
Original name Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR
Authors VÍCHA, Jan (203 Czech Republic, belonging to the institution), Michal STRAKA (203 Czech Republic, belonging to the institution), Markéta MUNZAROVÁ (203 Czech Republic, belonging to the institution) and Radek MAREK (203 Czech Republic, guarantor, belonging to the institution).
Edition Journal of Chemical Theory and Computation, Washington, American Chemical Society, 2014, 1549-9618.
Other information
Original language English
Type of outcome Article in a journal
Field of Study 10403 Physical chemistry
Country of publisher United States of America
Confidentiality degree is not subject to a state or trade secret
WWW DOI: 10.1021/ct400726y
Impact factor Impact factor: 5.498
RIV identification code RIV/00216224:14740/14:00073495
Organization unit Central European Institute of Technology
Doi http://dx.doi.org/10.1021/ct400726y
UT WoS 000334571900013
Keywords in English NMR shielding; spin-orbit coupling; d-orbitals; mechanism; transition-metal complex; iridium; EPR; g-tensor; A-tensor
Tags kontrola MP, rivok
Tags International impact, Reviewed
Changed by Changed by: Martina Prášilová, učo 342282. Changed: 26. 9. 2014 10:46.
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., those which contribute significantly to the sigmaSO. The correlation between the d-character of sigmaSO-active MOs and the size of the corresponding SO contribution to the nuclear magnetic shielding constant at LA is so tight that the magnitude of sigmaSO can be predicted in a given class of compounds on the basis of d-orbital character of relevant MO with relative error smaller than 15%. This correspondence is supported by an analogy between the perturbation theory expressions for the spin-orbit induced NMR sigma-tensor and those for the EPR g-tensor as well as the A-tensor of the ligand. This correlation is demonstrated on a series of d5 complexes of iridium. Thus, known qualitative relationships between electronic structure and EPR parameters can be newly applied to reproduce, predict, and understand the SO-induced contributions to NMR shielding constants of light atoms in heavy-atom compounds.
ED1.1.00/02.0068, research and development projectName: CEITEC - central european institute of technology
GAP206/12/0539, research and development projectName: Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy (Acronym: METALIN)
Investor: Czech Science Foundation
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