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dc.contributor.authorHopmann, Kathrin Helen
dc.contributor.authorMorello, Glenn Robert
dc.date.accessioned2017-10-12T09:06:11Z
dc.date.available2017-10-12T09:06:11Z
dc.date.issued2017-07-24
dc.description.abstractIron-PNP pincer complexes are efficient catalysts for the hydrogenation of aldehydes and ketones. A variety of hydrogenation mechanisms have been proposed for these systems, but there appears to be no clear consensus on a preferred pathway. We have employed high-level quantum chemical calculations to evaluate various mechanistic possibilities for iron-PNP catalysts containing either CH2, NCH3, or NH in the PNP linker. For all three catalyst types, we propose that the active species is a trans-dihydride complex. For CH2- and NH-containing complexes, we predict a dihydride mechanism involving a dearomatization of the backbone. The proposed mechanism proceeds through a metal-bound alkoxide intermediate, in excellent agreement with experimental observations. Interestingly, the relative stability of the ironalkoxide can explain why complexes with NCH3 in the PNP linker are chemoselective for aldehydes, whereas those with CH2 or NH in the linker do not show a clear substrate preference. As a general concept in computational catalysis, we recommend to employ known substrate selectivities as a diagnostic factor to evaluate the probability of proposed mechanisms.en_US
dc.descriptionSource at <a href=http://dx.doi.org/10.1021/acscatal.7b00764> http://dx.doi.org/10.1021/acscatal.7b00764 </a>en_US
dc.identifier.citationHopmann KH, Morello GR. A Dihydride Mechanism Can Explain the Intriguing Substrate Selectivity of Iron-PNP-Mediated Hydrogenation. ACS Catalysis. 2017en_US
dc.identifier.issn2155-5435
dc.identifier.otherFRIDAID 1483787
dc.identifier.otherhttp://dx.doi.org/10.1021/acscatal.7b00764
dc.identifier.urihttp://hdl.handle.net/10037/11656
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalACS Catalysis
dc.relation.projectIDTromsø forskningsstiftelse: TFS2016KHHen_US
dc.relation.projectIDNotur/NorStore: nn4654ken_US
dc.relation.projectIDNotur/NorStore: nn9330ken_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/SFF/179568/Norway/CTCC//en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/FRINATEK/231706/Norway/"EenyMeenyMinyMoe":Selectivity-determiningFactorsInAsymmetricCatalysis//en_US
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440::Teoretisk kjemi, kvantekjemi: 444en_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440::Theoretical chemistry, quantum chemistry: 444en_US
dc.titleA Dihydride Mechanism Can Explain the Intriguing Substrate Selectivity of Iron-PNP-Mediated Hydrogenationen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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