dc.contributor.author |
Bailey W. |
|
dc.contributor.author |
Phearman A. |
|
dc.contributor.author |
Luconi L. |
|
dc.contributor.author |
Rossin A. |
|
dc.contributor.author |
Yakhvarov D. |
|
dc.contributor.author |
D'Accolti L. |
|
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 |
2020-01-21T20:40:21Z |
|
dc.date.available |
2020-01-21T20:40:21Z |
|
dc.date.issued |
2019 |
|
dc.identifier.issn |
0947-6539 |
|
dc.identifier.uri |
https://dspace.kpfu.ru/xmlui/handle/net/157569 |
|
dc.description.abstract |
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The hydrogenolysis of mono- and dinuclear PdII hydroxides was investigated both experimentally and computationally. It was found that the dinuclear μ-hydroxide complexes {[(PCNR)Pd]2(μ-OH)}(OTf) (PCNH=1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole; PCNMe=1-[3-[(di-tert-butylphosphino)methyl]phenyl]-5-methyl-1H-pyrazole) react with H2 to form the analogous dinuclear hydride species {[(PCNR)Pd]2(μ-H)}(OTf). The dinuclear μ-hydride complexes were fully characterized, and are rare examples of structurally characterized unsupported singly bridged μ-H PdII dimers. The {[(PCNMe)Pd]2(μ-OH)}(OTf) hydrogenolysis mechanism was investigated through experiments and computations. The hydrogenolysis of the mononuclear complex (PCNH)Pd-OH resulted in a mixed ligand dinuclear species [(PCNH)Pd](μ-H)[(PCC)Pd] (PCC=a dianionic version of PCNH bound through phosphorus P, aryl C, and pyrazole C atoms) generated from initial ligand “rollover” C−H activation. Further exposure to H2 yields the bisphosphine Pd0 complex Pd[(H)PCNH]2. When the ligand was protected at the pyrazole 5-position in the (PCNMe)Pd−OH complex, no hydride formed under the same conditions; the reaction proceeded directly to the bisphosphine Pd0 complex Pd[(H)PCNMe]2. Reaction mechanisms for the hydrogenolysis of the monomeric and dimeric hydroxides are proposed. |
|
dc.relation.ispartofseries |
Chemistry - A European Journal |
|
dc.subject |
density functional calculations |
|
dc.subject |
hydrogen |
|
dc.subject |
hydrogenolysis |
|
dc.subject |
palladium |
|
dc.subject |
pincer complexes |
|
dc.title |
Hydrogenolysis of Dinuclear PCN<sup>R</sup> Ligated Pd<sup>II</sup> μ-Hydroxides and Their Mononuclear Pd<sup>II</sup> Hydroxide Analogues |
|
dc.type |
Article |
|
dc.relation.ispartofseries-issue |
42 |
|
dc.relation.ispartofseries-volume |
25 |
|
dc.collection |
Публикации сотрудников КФУ |
|
dc.relation.startpage |
9920 |
|
dc.source.id |
SCOPUS09476539-2019-25-42-SID85068524430 |
|