Show simple item record

dc.contributor.authorRehbein, Steven M.
dc.contributor.authorKania, Matthew J.
dc.contributor.authorNeufeldt, Sharon R.
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.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
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.publisherAmerican Chemical Societyen_US
dc.rightscopyright American Chemical Society 2021en_US
dc.subjectcomputational evaluationen_US
dc.subjectactivation of arenesen_US
dc.titleExperimental and Computational Evaluation of Tantalocene Hydrides for C–H Activation of Arenesen_US
mus.relation.collegeCollege of Letters & Scienceen_US
mus.relation.departmentChemistry & Biochemistry.en_US
mus.relation.universityMontana State University - Bozemanen_US

Files in this item


This item appears in the following Collection(s)

Show simple item record

MSU uses DSpace software, copyright © 2002-2017  Duraspace. For library collections that are not accessible, we are committed to providing reasonable accommodations and timely access to users with disabilities. For assistance, please submit an accessibility request for library material.