Vis enkel innførsel

dc.contributor.authorCastro, Abril C
dc.contributor.authorBalcells, David
dc.contributor.authorRepisky, Michal
dc.contributor.authorHelgaker, Trygve
dc.contributor.authorCascella, Michele
dc.date.accessioned2020-11-30T12:42:42Z
dc.date.available2020-11-30T12:42:42Z
dc.date.issued2020-11-23
dc.description.abstract<sup>1</sup>H NMR spectroscopy has become an important technique for the characterization of transition-metal hydride complexes, whose metal-bound hydrides are often difficult to locate by X-ray diffraction. In this regard, the accurate prediction of <sup>1</sup>H NMR chemical shifts provides a useful, but challenging, strategy to help in the interpretation of the experimental spectra. In this work, we establish a density-functional-theory protocol that includes relativistic, solvent, and dynamic effects at a high level of theory, allowing us to report an accurate and reliable interpretation of <sup>1</sup>H NMR hydride chemical shifts of iridium polyhydride complexes. In particular, we have studied in detail the hydride chemical shifts of the [Ir<sub>6</sub>(IMe)<sub>8</sub>(CO)<sub>2</sub>H<sub>14</sub>]<sup>2+</sup> complex in order to validate previous assignments. The computed <sup>1</sup>H NMR chemical shifts are strongly dependent on the relativistic treatment, the choice of the DFT exchange–correlation functional, and the conformational dynamics. By combining a fully relativistic four-component electronic-structure treatment with ab initio molecular dynamics, we were able to reliably model both the terminal and bridging hydride chemical shifts and to show that two NMR hydride signals were inversely assigned in the experiment.en_US
dc.identifier.citationCastro AC, Balcells D, Repisky M, Helgaker T, Cascella M. First-Principles Calculation of 1H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamics. Inorganic Chemistry. 2020en_US
dc.identifier.cristinIDFRIDAID 1853698
dc.identifier.doi10.1021/acs.inorgchem.0c02753
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/10037/19934
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalInorganic Chemistry
dc.relation.projectIDEC/H2020: 794563en_US
dc.relation.projectIDNotur/NorStore: NN4654Ken_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/SFF/262695/Norway/Hylleraas Centre for Quantum Molecular Sciences//en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/EC/ReaDy-NMR/794563/Norway/Relativistic and Dynamic effects in Computational NMR Spectroscopy of transition-metal complexes//en_US
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright © 2020 American Chemical Societyen_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.titleFirst-Principles Calculation of 1H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamicsen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


Tilhørende fil(er)

Thumbnail

Denne innførselen finnes i følgende samling(er)

Vis enkel innførsel