ID | 58597 |
フルテキストURL | |
著者 |
Ariyoshi, Keita
Department of Chemistry, Faculty of Science, Okayama University
Kotera, Mai
Department of Chemistry, Faculty of Science, Osaka University
Namioka, Atsushi
Department of Chemistry, Faculty of Science, Okayama University
Suzuki, Takayoshi
Department of Chemistry, Faculty of Science, Okayama University
ORCID
Kaken ID
publons
researchmap
|
抄録 | A reaction of [Cp*IrCl(Ph2Pqn)]PF6 {Cp* = η5-pentamethylcyclopentadienyl; Ph2Pqn = 8-(diphenylphosphino)quinoline} and Ag(CF3SO3) in methanol afforded orange crystals of the corresponding hydrido complex, [Cp*IrH(Ph2Pqn)]PF6, which was identified by 1H, 31P{1H} NMR and IR spectroscopy as well as X-ray structural analysis. The reactions in deuterated solvents indicated that formation of the hydrido complex proceeded via β-hydrogen elimination of the coordinated methanol molecule. It was also revealed that the hydrido formation was specific for the complex bearing Ph2Pqn ancillary ligand; the analogous complex with 1,2-bis(diphenylphosphino)benzene (diphos) or 1,10-phenanthroline (phen) did not give the corresponding hydrido complex by a similar reaction with Ag+ in methanol. In order to elucidate the reason for the different reactivity among these complexes, the crystal structures of the precursor chlorido complexes, [Cp*IrCl(Ph2Pqn)]PF6, [Cp*IrCl(diphos)]PF6 and [Cp*IrCl(phen)]PF6, as well as an acetonitrile complex of [Cp*Ir(Ph2Pqn)(CH3CN)](PF6)2, were also determined by X-ray analysis. The resulting structural information suggested that a specific formation of the hydrido complex with Ph2Pqn could be originated from the facile formation of the corresponding methanol complex and the hemilabile nature of ancillary Ph2Pqn ligand, which induced the reactivity of the coordinated methanol toward β-hydrogen elimination.
|
キーワード | 8-Quinolylphosphine
Hydrido complex
Ancillary ligand effect
β-Hydrogen elimination
Methanol complex
|
備考 | This fulltext is available in Jan. 2022.
|
発行日 | 2020-03-15
|
出版物タイトル |
Polyhedron
|
巻 | 179巻
|
出版者 | Elsevier
|
開始ページ | 114401
|
ISSN | 02775387
|
NCID | AA10531370
|
資料タイプ |
学術雑誌論文
|
言語 |
英語
|
OAI-PMH Set |
岡山大学
|
論文のバージョン | author
|
DOI | |
Web of Science KeyUT | |
関連URL | isVersionOf https://doi.org/10.1016/j.poly.2020.114401
|
助成機関名 |
Ministry of Education, Culture, Sports, Science and Technology
|
助成番号 | 18K05146
|