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EnglishChanging the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)(2) to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir-III to give Ir-V with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir-III, not Ir-V, because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. F-19,H-1-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)).
An anion-dependent switch in selectivity results from a change of C-H activation mechanism in the reaction of an imidazolium salt with IrH5(PPh3)(2) / L. N. Appelhans;D. Zuccaccia;A. Kovacevic;A. R. Chianese;J. R. Miecznikowski;A. Macchioni;E. Clot;O. Eisenstein;R. H. Crabtree. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 127(2005), pp. 16299-16311.
| Titolo: | An anion-dependent switch in selectivity results from a change of C-H activation mechanism in the reaction of an imidazolium salt with IrH5(PPh3)(2) | |
| Autori: | ||
| Data di pubblicazione: | 2005 | |
| Rivista: | ||
| Citazione: | An anion-dependent switch in selectivity results from a change of C-H activation mechanism in the reaction of an imidazolium salt with IrH5(PPh3)(2) / L. N. Appelhans;D. Zuccaccia;A. Kovacevic;A. R. Chianese;J. R. Miecznikowski;A. Macchioni;E. Clot;O. Eisenstein;R. H. Crabtree. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 127(2005), pp. 16299-16311. | |
| Abstract: | Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)(2) to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir-III to give Ir-V with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir-III, not Ir-V, because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. F-19,H-1-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)). | |
| Handle: | http://hdl.handle.net/11390/949782 | |
| Appare nelle tipologie: | 1.1 Articolo in rivista |
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