Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical
Shift in Transition-Metal Complexes: Linking NMR to EPR

J 2014

Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR

VÍCHA, Jan, Michal STRAKA, Markéta MUNZAROVÁ and Radek MAREK

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

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10403 Physical chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

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

Abstract

V originále

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.

Links

ED1.1.00/02.0068, research and development project

Name: CEITEC - central european institute of technology

GAP206/12/0539, research and development project

Name: Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy (Acronym: METALIN)

Investor: Czech Science Foundation

Files attached

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Citovat

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. Available from: https://dx.doi.org/10.1021/ct400726y.

@article{1165086,
   author = {Vícha, Jan and Straka, Michal and Munzarová, Markéta and Marek, Radek},
   article_location = {Washington},
   article_number = {4},
   doi = {http://dx.doi.org/10.1021/ct400726y},
   keywords = {NMR shielding; spin-orbit coupling; d-orbitals; mechanism; transition-metal complex; iridium; EPR; g-tensor; A-tensor},
   language = {eng},
   issn = {1549-9618},
   journal = {Journal of Chemical Theory and Computation},
   title = {Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR},
   url = {http://dx.doi.org/10.1021/ct400726y},
   volume = {10},
   year = {2014}
}

TY  - JOUR
ID  - 1165086
AU  - Vícha, Jan - Straka, Michal - Munzarová, Markéta - Marek, Radek
PY  - 2014
TI  - Mechanism of Spin-Orbit Effects on the Ligand NMR Chemical Shift in Transition-Metal Complexes: Linking NMR to EPR
JF  - Journal of Chemical Theory and Computation
VL  - 10
IS  - 4
SP  - 1489-1499
EP  - 1489-1499
PB  - American Chemical Society
SN  - 15499618
KW  - NMR shielding
KW  - spin-orbit coupling
KW  - d-orbitals
KW  - mechanism
KW  - transition-metal complex
KW  - iridium
KW  - EPR
KW  - g-tensor
KW  - A-tensor
UR  - http://dx.doi.org/10.1021/ct400726y
L2  - http://dx.doi.org/10.1021/ct400726y
N2  - 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.
ER  -

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. \textit{Journal of Chemical Theory and Computation}. Washington: American Chemical Society, 2014, vol.~10, No~4, p.~1489-1499. ISSN~1549-9618. Available from: https://dx.doi.org/10.1021/ct400726y.

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