Linking the Character of the Metal-Ligand Bond to the Ligand NMR Shielding in Transition-Metal Complexes: NMR Contributions from Spin-Orbit Coupling

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F70883521%3A28610%2F17%3A63516066" target="_blank" >RIV/70883521:28610/17:63516066 - isvavai.cz</a>

Alternative codes found

RIV/61388963:_____/17:00478265 RIV/00216224:14740/17:00094827

Result on the web

<a href="http://dx.doi.org/10.1021/acs.jctc.7b00444" target="_blank" >http://dx.doi.org/10.1021/acs.jctc.7b00444</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.7b00444" target="_blank" >10.1021/acs.jctc.7b00444</a>

Result language

angličtina

Original language name

Linking the Character of the Metal-Ligand Bond to the Ligand NMR Shielding in Transition-Metal Complexes: NMR Contributions from Spin-Orbit Coupling

Original language description

Relativistic effects significantly affect various spectroscopic properties of compounds containing heavy elements. Particularly in Nuclear Magnetic Resonance (NMR) spectroscopy, the heavy atoms strongly influence the NMR shielding constants of neighboring light atoms. In this account we analyze paramagnetic contributions to NMR shielding constants and their modulation by relativistic spin-orbit effects in a series of transition-metal complexes of Pt(II), Au(I), Au(III), and Hg(II). We show how the paramagnetic NMR shielding and spin-orbit effects relate to the character of the metal-ligand (M-L) bond. A correlation between the (back)-donation character of the M-L bond in d10 Au(I) complexes and the propagation of the spin-orbit (SO) effects from M to L through the M-L bond influencing the ligand NMR shielding via the Fermi-contact mechanism is found and rationalized by using third-order perturbation theory. The SO effects on the ligand NMR shielding are demonstrated to be driven by both the electronic structure of M and the nature of the trans ligand, sharing the σ-bonding metal orbital with the NMR spectator atom L. The deshielding paramagnetic contribution is linked to the σ-type M-L bonding orbitals, which are notably affected by the trans ligand. The SO deshielding role of σ-type orbitals is enhanced in d10 Hg(II) complexes with the Hg 6p atomic orbital involved in the M-L bonding. In contrast, in d8 Pt(II) complexes, occupied π-type orbitals play a dominant role in the SO-altered magnetic couplings due to the accessibility of vacant antibonding σ-type MOs in formally open 5d-shell (d8). This results in a significant SO shielding at the light atom. The energy- and composition-modulation of σ- vs π-type orbitals by spin-orbit coupling is rationalized and supported by visualizing the SO-induced changes in the electron density around the metal and light atoms (spin-orbit electron deformation density, SO-EDD).

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

—

Volume of the periodical

13

Issue of the periodical within the volume

8

Country of publishing house

US - UNITED STATES

Number of pages

16

Pages from-to

3586-3601

UT code for WoS article

000407522100013

EID of the result in the Scopus database

2-s2.0-85027241605