Understanding the electronic factors responsible for ligand
spin-orbit NMR shielding in transition-metal complexes

J 2015

Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes

VÍCHA, Jan; Cina FOROUTANNEJAD; Tomasz PAWLAK; Markéta MUNZAROVÁ; Michal STRAKA et al.

Základní údaje

Originální název

Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes

Autoři

VÍCHA, Jan; Cina FOROUTANNEJAD; Tomasz PAWLAK; Markéta MUNZAROVÁ; Michal STRAKA a Radek MAREK

Vydání

Journal of Chemical Theory and Computation, Washington D.C. American Chemical Society, 2015, 1549-9618

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/ct501089z

Impakt faktor

Impact factor: 5.301

Kód RIV

RIV/00216224:14740/15:00080688

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1021/ct501089z

UT WoS

000353176500018

EID Scopus

2-s2.0-84927772993

Klíčová slova anglicky

NMR; spin-orbit; nuclear magnetic shielding; chemical bonding; gold; platinum

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 22. 3. 2016 13:18, Mgr. Eva Špillingová

Anotace

V originále

The significant role of the relativistic effects in altering the NMR chemical shifts of light nuclei in heavy-element compounds has been recognized for a long time, however full understanding of this phenomenon in relation to the electronic structure has not been achieved. In this study, the recently observed qualitative differences between the platinum and gold compounds in the magnitude and the sign of spin-orbit-induced (SO) nuclear magnetic shielding at the vicinal light atom (13C, 15N), sigmaSO(LA), are explained by the contractions of 6s and 6p atomic orbitals in Au complexes, originating in the larger Au nuclear charge and stronger scalar relativistic effects in gold complexes. This leads to the chemical activation of metal 6s and 6p atomic orbitals in Au complexes and their larger participation in bonding with the ligand, which modulates the propagation of metal-induced SO effects on the NMR signal of the LA via the Spin-Orbit/Fermi Contact (SO/FC) mechanism. The magnitude of the sigmaSO(LA) in these square-planar complexes can be understood on the basis of a balance between various metal-based 5d-5d* and 6p-6p* orbital magnetic couplings. The large and positive sigmaSO(LA) in platinum complexes is dominated by the shielding platinum-based 5d-5d* magnetic couplings whereas small or negative sigmaSO(LA) in gold complexes is related to the deshielding contribution of the gold-based 6p-6p* magnetic couplings. Further, it is demonstrated that sigmaSO(LA) correlates quantitatively with the extent of M–LA electron sharing that is the covalence of the M–LA bond (characterized by the QTAIM delocalization index, DI). Present findings will contribute to further understanding of the origin and propagation of the relativistic effects influencing the experimental NMR parameters in heavy-element systems.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

EE2.3.30.0009, projekt VaV

Název: Zaměstnáním čerstvých absolventů doktorského studia k vědecké excelenci

GAP206/12/0539, projekt VaV

Název: Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy (Akronym: METALIN)

Investor: Grantová agentura ČR, Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy

4SGA8546, interní kód MU

Název: Towards the graphene selective receptors: the role of electric field in non-covalent interactions (Akronym: GrapheneReceptor)

Investor: Jihomoravský kraj, Towards the graphene selective receptors: the role of electric field in non-covalent interactions, Granty pro zahraniční vědce

Přiložené soubory

JCTC15_11_1509_ct501089z.pdf

Požádat o autorskou verzi souboru

Citovat

VÍCHA, Jan; Cina FOROUTANNEJAD; Tomasz PAWLAK; Markéta MUNZAROVÁ; Michal STRAKA a Radek MAREK. Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes. Journal of Chemical Theory and Computation. Washington D.C.: American Chemical Society, 2015, roč. 11, č. 4, s. 1509-1517. ISSN 1549-9618. Dostupné z: https://doi.org/10.1021/ct501089z.

@article{1229123,
   author = {Vícha, Jan and Foroutannejad, Cina and Pawlak, Tomasz and Munzarová, Markéta and Straka, Michal and Marek, Radek},
   article_location = {Washington D.C.},
   article_number = {4},
   doi = {https://doi.org/10.1021/ct501089z},
   keywords = {NMR; spin-orbit; nuclear magnetic shielding; chemical bonding; gold; platinum},
   language = {eng},
   issn = {1549-9618},
   journal = {Journal of Chemical Theory and Computation},
   title = {Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes},
   url = {http://dx.doi.org/10.1021/ct501089z},
   volume = {11},
   year = {2015}
}

TY  - JOUR
ID  - 1229123
AU  - Vícha, Jan - Foroutannejad, Cina - Pawlak, Tomasz - Munzarová, Markéta - Straka, Michal - Marek, Radek
PY  - 2015
TI  - Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes
JF  - Journal of Chemical Theory and Computation
VL  - 11
IS  - 4
SP  - 1509-1517
EP  - 1509-1517
PB  - American Chemical Society
SN  - 15499618
KW  - NMR
KW  - spin-orbit
KW  - nuclear magnetic shielding
KW  - chemical bonding
KW  - gold
KW  - platinum
UR  - http://dx.doi.org/10.1021/ct501089z
L2  - http://dx.doi.org/10.1021/ct501089z
N2  - The significant role of the relativistic effects in altering the NMR chemical shifts of light nuclei in heavy-element compounds has been recognized for a long time, however full understanding of this phenomenon in relation to the electronic structure has not been achieved. In this study, the recently observed qualitative differences between the platinum and gold compounds in the magnitude and the sign of spin-orbit-induced (SO) nuclear magnetic shielding at the vicinal light atom (13C, 15N), sigmaSO(LA), are explained by the contractions of 6s and 6p atomic orbitals in Au complexes, originating in the larger Au nuclear charge and stronger scalar relativistic effects in gold complexes. This leads to the chemical activation of metal 6s and 6p atomic orbitals in Au complexes and their larger participation in bonding with the ligand, which modulates the propagation of metal-induced SO effects on the NMR signal of the LA via the Spin-Orbit/Fermi Contact (SO/FC) mechanism. The magnitude of the sigmaSO(LA) in these square-planar complexes can be understood on the basis of a balance between various metal-based 5d-5d* and 6p-6p* orbital magnetic couplings. The large and positive sigmaSO(LA) in platinum complexes is dominated by the shielding platinum-based 5d-5d* magnetic couplings whereas small or negative sigmaSO(LA) in gold complexes is related to the deshielding contribution of the gold-based 6p-6p* magnetic couplings. Further, it is demonstrated that sigmaSO(LA) correlates quantitatively with the extent of M–LA electron sharing that is the covalence of the M–LA bond (characterized by the QTAIM delocalization index, DI). Present findings will contribute to further understanding of the origin and propagation of the relativistic effects influencing the experimental NMR parameters in heavy-element systems.
ER  -

VÍCHA, Jan; Cina FOROUTANNEJAD; Tomasz PAWLAK; Markéta MUNZAROVÁ; Michal STRAKA a Radek MAREK. Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes. \textit{Journal of Chemical Theory and Computation}. Washington D.C.: American Chemical Society, 2015, roč.~11, č.~4, s.~1509-1517. ISSN~1549-9618. Dostupné z: https://doi.org/10.1021/ct501089z.

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