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Theoretical studies of inorganic and organometallic reaction mechanisms. 14. beta-hydrogen transfer and alkene/alkyne insertion at a cationic iridium center
dc.creator | Niu, SQ | |
dc.creator | Zarić, Snežana D. | |
dc.creator | Bayse, CA | |
dc.creator | Strout, DL | |
dc.creator | Hall, Michael B. | |
dc.date.accessioned | 2018-11-22T00:02:22Z | |
dc.date.available | 2018-11-22T00:02:22Z | |
dc.date.issued | 1998 | |
dc.identifier.issn | 0276-7333 | |
dc.identifier.uri | https://cherry.chem.bg.ac.rs/handle/123456789/399 | |
dc.description.abstract | Recent experimental work shows that alkanes can be activated by Cp*Ir(PMe3)(CH3)(+) at room temperature to generate olefin complexes. The reaction begins with alkane activation by oxidative addition (OA) followed by reductive elimination (RE) of methane and then olefin formation by the beta-H transfer from the bound alkyl. Ab initio calculations and density functional theory (DFT) studies of ethane activation by CpIr(PH3)(CH3)(+) (1) to generate CpIr(PH3)(eta(2)-C2H4)(H)(+) (7) show that the beta-H transfer from CpIr(PH3)(C2H5)(+) (5) to 7 is exothermic by 12 and 16 kcal/mol with a very low barrier of 0.7 and 0.4 kcal/mol at the DFT and CCSD levels, respectively. Thus, the rate-determining step in alkane dehydrogenation to olefin complexes by Cp*Ir(PMe3)(CH3)(+) is the alkane OA step. These results are in very good agreement with the experimental work of Bergman and co-workers. A strong stabilizing interaction between either ethylene or acetylene and CpIr(PH3)(CH3)(+) leads to high activation barriers (25-36 kcal/mol) for the insertion processes of ethylene or acetylene. In comparison to ethylene, the insertion reaction of acetylene with the CpIr(PH3)(CH3)(+) complex is more favorable. Thus, the dimerization of terminal alkynes catalyzed by cationic iridium complexes is plausible. | en |
dc.publisher | Amer Chemical Soc, Washington | |
dc.rights | restrictedAccess | |
dc.source | Organometallics | |
dc.title | Theoretical studies of inorganic and organometallic reaction mechanisms. 14. beta-hydrogen transfer and alkene/alkyne insertion at a cationic iridium center | en |
dc.type | article | |
dc.rights.license | ARR | |
dcterms.abstract | Зарић, Снежана; Ниу, СQ; Баyсе, ЦA; Халл, МБ; Строут, ДЛ; | |
dc.citation.volume | 17 | |
dc.citation.issue | 23 | |
dc.citation.spage | 5139 | |
dc.citation.epage | 5147 | |
dc.identifier.wos | 000077119200030 | |
dc.identifier.doi | 10.1021/om980429n | |
dc.citation.other | 17(23): 5139-5147 | |
dc.citation.rank | M21 | |
dc.type.version | publishedVersion | en |
dc.identifier.scopus | 2-s2.0-0001393768 |