Four-Component Relativistic 31P NMR Calculations for trans Platinum(II) Complexes: Importance of the Solvent and Dynamics in Spectral Simulations
dc.contributor.author
dc.date.accessioned
2023-03-28T13:47:33Z
dc.date.available
2023-03-28T13:47:33Z
dc.date.issued
2019-06-21
dc.identifier.issn
1477-9226
dc.identifier.uri
dc.description.abstract
We report a combined experimental-theoretical study on the 31P NMR chemical shift for a number of trans platinum(II) complexes. Validity and reliability of the 31P NMR chemical shift calculations are examined by comparing with the experimental data. A successful computational protocol for the accurate prediction of the 31P NMR chemical shifts was established for trans [PtCl2(dma)PPh3] (dma = dimethylamine) complex. The reliability of the computed values is shown to be critically dependent on the level of relativistic effects (two-component vs. four component), choice of density functional, dynamical averaging, and solvation effects. Snapshots from ab initio molecular dynamics simulations were used to identify those solvent molecules which show the largest interactions with the platinum complex, through inspection by the non-covalent interaction program. We observe satisfactory accuracy from the full four-component matrix Dirac-Kohn-Sham method (mDKS) based on the Dirac-Coulomb Hamiltonian, in conjunction with the KT2 density functional, and dynamical averaging with explicit solvent molecules
dc.description.sponsorship
The following organizations are thanked for financial support:
the Ministerio de Ciencia e Innovación (MICINN, PhDscholarship BES-2012-052792), the Consejo Nacional de Ciencia
y Tecnología (CONACyT), the Ministerio de Economía y
Competitividad (MINECO, CTQ2014-59212-P, CTQ2015-70851-
ERC, CTQ2015-68779-R, and CTQ2017-87392-P), GenCat
(2014SGR1202 and XRQTC network), European Fund for
Regional Development (FEDER, UNGI10-4E-801), and the Slovak
Grant Agency VEGA (contract no. 2/0116/17). This work was
supported by the Norwegian Research Council through the CoE
Hylleraas Centre for Quantum Molecular Sciences Grant
262695, 231571/F20, and 214095/F20. This work has received
support from the Norwegian Supercomputing Program
(NOTUR) through a grant of computer time (NN4654K)
dc.format.extent
8 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1039/c9dt00570f
dc.relation.ispartof
© Dalton Transactions, 2019, vol. 48, núm. 23, p. 8076-8083
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
Castro Aguilera, Abril Carolina Fliegl, Heike Cascella, Michele Helgaker, Trygve Repisky, Michal Komorovsky, Stanislav Medrano, María Ángeles Gómez Quiroga, Adoración Swart, Marcel 2019 Four-Component Relativistic 31P NMR Calculations for trans Platinum(II) Complexes: Importance of the Solvent and Dynamics in Spectral Simulations Dalton Transactions 48 23 8076 8083
dc.subject
dc.title
Four-Component Relativistic 31P NMR Calculations for trans Platinum(II) Complexes: Importance of the Solvent and Dynamics in Spectral Simulations
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
029953
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1477-9234