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dc.contributor.authorHopmann, Kathrin Helen
dc.date.accessioned2017-03-08T15:34:16Z
dc.date.available2017-03-08T15:34:16Z
dc.date.issued2016-09-27
dc.description.abstractIridium chemistry is versatile and widespread, with superior performance for reaction types such as enantioselective hydrogenation and C−H activation. In order to gain insight into the mechanistic details of such systems, density functional theory (DFT) studies are often employed. But how accurate is DFT for modeling iridium-mediated transformations in solution? We have evaluated how well DFT reproduces the energies and reactivities of 11 iridium-mediated transformations, which were carefully chosen to correspond to elementary steps typically encountered in iridium-catalyzed chemistry (bond formation, isomerization, ligand substitution, and ligand association). Five DFT functionals, B3LYP, PBE, PBE0, M06L, and M11L, were evaluated as-is or in combination with an empirical dispersion correction (D2, D3, or D3BJ), leading to 13 combinations. Different solvent models (IEFPCM and SMD) were evaluated, alongside various correction terms such as big basis set effects, counterpoise corrections, frequency scaling, and different entropy modifications. PBE-D type functionals are clearly superior, with PBE-D2,IEFPCM providing average absolute errors for uncorrected Gibbs free energies of 0.9 kcal/mol for the nine reactions with a constant number of moles (1.2 kcal/mol for all 11 reactions). This provides a straightforward and accurate computational protocol for computing free energies of iridium-mediated transformations in solution. However, because the good results may originate from favorable error cancellations of larger and oppositely signed enthalpy and entropy errors, this protocol is recommended for free energies only.en_US
dc.description.sponsorshipThis work has been supported by the Research Council of Norway through a FRIPRO grant (No. 231706/F20) to K.H.H., through a Centre of Excellence Grant (No. 179568/ V30) and by Notur - The Norwegian Metacenter for Computational Science through a grant of computer time (No. nn9330k).en_US
dc.descriptionPublished version. Source at <a href=http://doi.org/10.1021/acs.organomet.6b00377>http://doi.org/10.1021/acs.organomet.6b00377</a>. License - <a href=http://pubs.acs.org/page/policy/authorchoice_termsofuse.html>ACS AuthorChoice</a>.en_US
dc.identifier.citationHopmann KH. How accurate is DFT for iridium-mediated chemistry?. Organometallics. 2016;35(22):3795-3807en_US
dc.identifier.cristinIDFRIDAID 1379893
dc.identifier.doi10.1021/acs.organomet.6b00377
dc.identifier.issn0276-7333
dc.identifier.issn1520-6041
dc.identifier.urihttps://hdl.handle.net/10037/10489
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalOrganometallics
dc.relation.projectIDNotur/NorStore: nn9330ken_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN//179568/Norway///en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN//231706/Norway///en_US
dc.relation.urihttp://pubs.acs.org/doi/abs/10.1021/acs.organomet.6b00377
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.titleHow accurate is DFT for iridium-mediated chemistry?en_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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