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Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma
dc.creator | Pitts, Amanda L. | |
dc.creator | Wriglesworth, Alisdair | |
dc.creator | Sun, Xue-Zhong | |
dc.creator | Calladine, James A. | |
dc.creator | Zarić, Snežana D. | |
dc.creator | George, Michael W. | |
dc.creator | Hall, Michael B. | |
dc.date.accessioned | 2018-11-22T00:28:12Z | |
dc.date.available | 2018-11-22T00:28:12Z | |
dc.date.issued | 2014 | |
dc.identifier.issn | 0002-7863 | |
dc.identifier.uri | https://cherry.chem.bg.ac.rs/handle/123456789/1792 | |
dc.description.abstract | Carbon-hydrogen bond activation reactions of four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) by the Cp'Rh(CO) fragments (Cp' = eta(5)-C5H5 (Cp) or eta(5)-C5Me5 (Cp*)) were modeled theoretically by combining density functional and coupled cluster theories, and their reaction rates were measured by fast time-resolved infrared spectroscopy. The reaction has two steps, starting with the formation of a a-complex intermediate, followed by oxidative addition of the C-H bond by the rhodium. A range of a-complex stabilities among the electronically unique C-H bonds in a cycloalkane were calculated and are related to the individual strengths of the C-H bond's interactions with the Rh fragment and the steric repulsion that is incurred upon forming the specific a-complex. The unexpectedly large increase in the lifetimes of the a-complexes from cyclohexane to cycloheptane was predicted to be due to the large range of stabilities of the different sigma-complexes found for cycloheptane.. The reaction lifetimes were simulated with two mechanisms, with and without migrations among the different complexes, to determine if ring migrations prior to C-H activation were influencing the rate. Both mechanisms predicted similar lifetimes for cyclopentane, cyclohexane, and, to a lesser extent, cycloheptane, suggesting ring migrations do not have a large impact on the rate of C-H activation for these cycloalkanes. For cyclooctane, the inclusion of ring migrations in the reaction mechanism led to a more accurate prediction of the lifetime, indicating that ring migrations did have an effect on the rate of C-H activation for this alkane, and that migration among the a-complexes is faster than the C-H activation for this larger cycloalkane. | en |
dc.publisher | Amer Chemical Soc, Washington | |
dc.relation | Royal Society | |
dc.relation | University of Nottingham | |
dc.relation | National Science Foundation [CHE 0910552, 1300787] | |
dc.rights | restrictedAccess | |
dc.source | Journal of the American Chemical Society | |
dc.title | Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma | en |
dc.type | article | |
dc.rights.license | ARR | |
dcterms.abstract | Цалладине, Јамес A.; Зарић, Снежана; Wриглесwортх, Aлисдаир; Питтс, Aманда Л.; Георге, Мицхаел W.; Сун, Xуе-Зхонг; Халл, Мицхаел Б.; | |
dc.citation.volume | 136 | |
dc.citation.issue | 24 | |
dc.citation.spage | 8614 | |
dc.citation.epage | 8625 | |
dc.identifier.wos | 000337720200025 | |
dc.identifier.doi | 10.1021/ja5014773 | |
dc.citation.other | 136(24): 8614-8625 | |
dc.citation.rank | aM21 | |
dc.identifier.pmid | 24823385 | |
dc.description.other | Supplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/3685] | |
dc.type.version | publishedVersion | en |
dc.identifier.scopus | 2-s2.0-84902687617 |