Complexation of the (畏5-Cp)Ru+ and (畏5-Cp*)Ru+ Arenophiles on Alkynylnaphthalene: Solvent Effect on the Regioselectivity and the Haptotropic Rearrangement

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• 作者：Rim Makhoul ; Jennifer A. Shaw-Taberlet ; Hiba Sahnoune ; Vincent Dorcet ; Samia Kahlal ; Jean-Fran莽ois Halet ; Jean-Ren茅 Hamon ; Claude Lapinte
• 刊名：Organometallics
• 出版年：2014
• 出版时间：November 10, 2014
• 年：2014
• 卷：33
• 期：21
• 页码：6023-6032
• 全文大小：425K
• ISSN：1520-6041

文摘

The reactions of [Cp*Ru(NCMe)₃](PF₆) and 1,4-R-C₆H₄-C鈮-SiMe₃ (R = Me, C鈮-SiMe₃; Cp* = 畏⁵-C₅Me₅) in CH₂Cl₂ provided the complexes [Cp*Ru(畏⁶-4-MeC₆H₄-C鈮-SiMe₃)](PF₆) (1) and [Cp*Ru(畏⁶-1,4-C₆H₄(C鈮-SiMe₃)₂](PF₆) (2) in 65% yield. A similar reaction using 1-(trimethylsilylethynyl)naphthalene provided the complexes [Cp*Ru(畏⁶-C₁₀H₇(C鈮-SiMe₃))](PF₆), bearing the Cp*Ru⁺ arenophile on the monosubstituted (3A) or unsubstituted (3B) fused ring, in 86% yield. The 3A/3B kinetic ratio is 43/57, while the 3A/3B thermodynamic ratio is 27/73. The bis(alkynylnaphthalene) complexes [Cp*Ru(畏⁶-1,4-C₁₀H₆(C鈮-SiMe₃)₂)](PF₆) were also obtained in good yields with 4A/4B kinetic ratios ranging from 80/20 to 16/84 depending on the concentration of a labile ligand able to temporarily replace one acetonitrile ligand on [Cp*Ru(NCMe)₃](PF₆). In the absence of such a ligand the reaction did not take place. Isomer 4A can be quantitatively converted to the thermodynamic regioisomer 4B. The kinetic products were obtained in less than 4 h at temperatures ranging from 鈭?7 to 20 掳C, while the isomerization is much slower. The thermodynamic equilibrium is reached after several days at 20 掳C in a good coordinating solvent such as acetone. The bis(alkynylnaphthalene) was also reacted with [CpRu(NCMe)₃](PF₆) (Cp = 畏⁵-C₅H₅). The corresponding complexes 5A,B were isolated with an overall yield of 87% and 5A/5B kinetic ratios ranging from 5/95 to 20/80, while the thermodynamic ratio was 45/55. The experimental data analyzed with the support of theoretical calculations allowed us to propose a mechanism for the reactions of complexation and isomerization.