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Pyrazole-Based PCN Pincer Complexes of Palladium(II): Mono- and Dinuclear Hydroxide Complexes and Ligand Rollover C-H Activation

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dc.contributor.author Bailey W.
dc.contributor.author Luconi L.
dc.contributor.author Rossin A.
dc.contributor.author Yakhvarov D.
dc.contributor.author Flowers S.
dc.contributor.author Kaminsky W.
dc.contributor.author Kemp R.
dc.contributor.author Giambastiani G.
dc.contributor.author Goldberg K.
dc.date.accessioned 2018-09-18T20:07:46Z
dc.date.available 2018-09-18T20:07:46Z
dc.date.issued 2015
dc.identifier.issn 0276-7333
dc.identifier.uri https://dspace.kpfu.ru/xmlui/handle/net/136791
dc.description.abstract © 2015 American Chemical Society. Palladium complexes of the novel unsymmetrical phosphine pyrazole-containing pincer ligands PCN<sup>H</sup> (PCN<sup>H</sup> = 1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole) and PCN<sup>Me</sup> (PCN<sup>Me</sup> = 1-[3-[(di-tert-butylphosphino)methyl]phenyl]-5-methyl-1H-pyrazole) have been prepared and characterized through single-crystal X-ray diffraction and multinuclear <sup>1</sup>H, <sup>13</sup>C{<sup>1</sup>H}, and <sup>31</sup>P{<sup>1</sup>H} NMR spectroscopy. In preparations of the monomeric hydroxide species (PCN<sup>H</sup>)Pd(OH), an unexpected N detachment followed by C-H activation on the heterocycle 5-position took place resulting in conversion of the monoanionic {P,C<sup>-</sup>,N} framework into a dianionic {P,C<sup>-</sup>,C<sup>-</sup>} ligand set. The dinuclear hydroxide-bridged species (PCN<sup>H</sup>)Pd(μ-OH)Pd(PCC) was the final product obtained under ambient conditions. The "rollover" activation was followed via <sup>31</sup>P{<sup>1</sup>H} NMR spectroscopy, and dinuclear cationic μ-OH and monomeric Pd<sup>II</sup> hydroxide intermediates were identified. DFT computational analysis of the process (M06//6-31G∗, THF) showed that the energy barriers for the pyrazolyl rollover and for C-H activation through a σ-bond metathesis reaction are low enough to be overcome under ambient-temperature conditions, in line with the experimental findings. In contrast to the PCN<sup>H</sup> system, no "rollover" reactivity was observed in the PCN<sup>Me</sup> system, and the terminal hydroxide complex (PCN<sup>Me</sup>)Pd(OH) could be readily isolated and fully characterized. (Chemical Equation Presented).
dc.relation.ispartofseries Organometallics
dc.title Pyrazole-Based PCN Pincer Complexes of Palladium(II): Mono- and Dinuclear Hydroxide Complexes and Ligand Rollover C-H Activation
dc.type Article
dc.relation.ispartofseries-issue 16
dc.relation.ispartofseries-volume 34
dc.collection Публикации сотрудников КФУ
dc.relation.startpage 3998
dc.source.id SCOPUS02767333-2015-34-16-SID84940213856


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  • Публикации сотрудников КФУ Scopus [24551]
    Коллекция содержит публикации сотрудников Казанского федерального (до 2010 года Казанского государственного) университета, проиндексированные в БД Scopus, начиная с 1970г.

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