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dc.contributor.authorNovotný, Jan
dc.contributor.authorVícha, Jan
dc.contributor.authorBora, Pankaj L.
dc.contributor.authorRepisky, Michal
dc.contributor.authorStraka, Michal
dc.contributor.authorKomorovsky, Stanislav
dc.contributor.authorMarek, Radek
dc.date.accessioned2018-07-30T09:21:29Z
dc.date.available2018-07-30T09:21:29Z
dc.date.issued2017-07-06
dc.description.abstractRelativistic 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).en_US
dc.description.sponsorshipThe Czech Science Foundation The Ministry of Education, Youth and Sports of the Czech Republic SASPRO Program Notur/NorStoreen_US
dc.descriptionThis document appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see <a href=https://doi.org/10.1021/acs.jctc.7b00444> https://doi.org/10.1021/acs.jctc.7b00444</a>.en_US
dc.identifier.citationNovotný, J., Vícha, J., Bora, P.L., Repisky, M., Straka, M., Komorovsky, S. & Marek, R. (2017). Linking the Character of the Metal-Ligand Bond to the Ligand NMR Shielding in Transition-Metal Complexes: NMR Contributions from Spin-Orbit Coupling. Journal of Chemical Theory and Computation, 13(8), 3586-3601. https://doi.org/10.1021/acs.jctc.7b00444en_US
dc.identifier.cristinIDFRIDAID 1544397
dc.identifier.doi10.1021/acs.jctc.7b00444
dc.identifier.issn1549-9618
dc.identifier.issn1549-9626
dc.identifier.urihttps://hdl.handle.net/10037/13301
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalJournal of Chemical Theory and Computation
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/SFF/179568/Norway/Centre for Theoretical and Computational Chemistry/CTCC/en_US
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.titleLinking the Character of the Metal-Ligand Bond to the Ligand NMR Shielding in Transition-Metal Complexes: NMR Contributions from Spin-Orbit Couplingen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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