Osmium−Allenylidene Complexes Containing an N-Heterocyclic Carbene Ligand

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• 作者：Ricardo Castarlenas ; Miguel A. Esteruelas ; Ralte Lalrempuia ; Montserrat Olivá ; n ; Enrique O&#xf1 ; ate
• 刊名：Organometallics
• 出版年：2008
• 出版时间：February 25, 2008
• 年：2008
• 卷：27
• 期：4
• 页码：795 - 798
• 全文大小：128K
• 年卷期：v.27,no.4(February 25, 2008)
• ISSN：1520-6041

文摘

Complex [(η⁶-p-cymene)OsCl(IPr)]OTf (1) reacts with 1,1-diphenyl-2-propyn-1-ol to afford the hydroxyvinylidene derivative [(η⁶-p-cymene)OsCl{acs.org/images/entities/dbd_2.gif">Cacs.org/images/entities/dbd_2.gif">CHC(OH)Ph₂}(IPr)]OTf (2), which dehydrates to form [(η⁶-p-cymene)OsCl(acs.org/images/entities/dbd_2.gif">Cacs.org/images/entities/dbd_2.gif">Cacs.org/images/entities/dbd_2.gif">CPh₂)(IPr)]OTf (3). Treatment in acetonitrile under reflux of the BF₄-salt of 3 with AgBF₄ leads to the tetrakis(solvento) derivative [Os(acs.org/images/entities/dbd_2.gif">Cacs.org/images/entities/dbd_2.gif">Cacs.org/images/entities/dbd_2.gif">CPh₂)(CH₃CN)₄(IPr)][BF₄]₂ (4). At 95 °C, the addition of PⁱPr₃ to an acetonitrile solution of 4 yields the dicationic mixed PⁱPr₃-IPr osmium−allenylidene complex [Os(acs.org/images/entities/dbd_2.gif">Cacs.org/images/entities/dbd_2.gif">Cacs.org/images/entities/dbd_2.gif">CPh₂)(CH₃CN)₃(IPr)(PⁱPr₃)][BF₄]₂ (5), which in 2-propanol and in the presence of NaCl evolves into the five-coordinate hydride−alkenylcarbyne [OsHCl(acs.org/images/entities/tbd1.gif">CCHacs.org/images/entities/dbd_2.gif">CPh₂)(IPr)(PⁱPr₃)][BF₄] (6). The X-ray structures of 2, 5, and 6 are also reported.