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dc.contributor.authorRehbein, Steven M.
dc.contributor.authorKania, Matthew J.
dc.contributor.authorNeufeldt, Sharon R.
dc.date.accessioned2022-09-26T21:48:38Z
dc.date.available2022-09-26T21:48:38Z
dc.date.issued2021-08
dc.identifier.citationRehbein, S. M., Kania, M. J., & Neufeldt, S. R. (2021). Experimental and Computational Evaluation of Tantalocene Hydrides for C–H Activation of Arenes. Organometallics, 40(15), 2666-2677.en_US
dc.identifier.issn0276-7333
dc.identifier.urihttps://scholarworks.montana.edu/xmlui/handle/1/17231
dc.descriptionThis document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Organometallics, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.organomet.1c00308en_US
dc.description.abstractHalf a century ago, tantalocene hydrides (especially Cp2TaH3, where Cp = η5-C5H5) were reported to catalyze H/D exchange with arenes. However, there has been very little follow-up to the seminal reports, and numerous questions about this chemistry remain unanswered. In an effort to better evaluate the potential of tantalocene hydrides for processes involving C–H activation, we have conducted a series of experimental and computational studies on these complexes. Density functional theory (DFT) calculations support a mechanism for arene C–H activation involving oxidative addition at transient TaIII, rather than a σ-bond metathesis mechanism at TaV. Comparisons were made between thermal and photochemical conditions for the reaction of Cp2TaH3 with benzene-d6, and H/D exchange was found to be moderately faster under thermal conditions. In a reaction with toluene, Cp2TaH3 activates the aromatic C(sp2)–H bonds but not the benzylic bonds. DFT calculations suggest that benzylic C–H activation at TaIII has a barrier similar to aromatic C–H activation, but that formation of a π-complex with Cp2TaH directs preferential aromatic C–H activation. Analogous complexes containing the less labile permethylated ligand Cp* (Cp* = η5-C5Me5) were also evaluated for their ability to catalyze H/D exchange with benzene-d6, but these complexes are less active than Cp2TaH3. DFT calculations indicate that the methyl groups of Cp* disfavor π-coordination of an arene to the TaIII intermediate.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightscopyright American Chemical Society 2021en_US
dc.rights.urihttp://web.archive.org/web/20190502075603/http://pubs.acs.org/paragonplus/copyright/jpa_form_a.pdfen_US
dc.subjectcomputational evaluationen_US
dc.subjecthydridesen_US
dc.subjectactivation of arenesen_US
dc.titleExperimental and Computational Evaluation of Tantalocene Hydrides for C–H Activation of Arenesen_US
dc.typeArticleen_US
mus.citation.extentfirstpage1en_US
mus.citation.extentlastpage14en_US
mus.citation.issue15en_US
mus.citation.journaltitleOrganometallicsen_US
mus.citation.volume40en_US
mus.identifier.doi10.1021/acs.organomet.1c00308en_US
mus.relation.collegeCollege of Letters & Scienceen_US
mus.relation.departmentChemistry & Biochemistry.en_US
mus.relation.universityMontana State University - Bozemanen_US
mus.data.thumbpage7en_US


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