Complexation of the (η5-​Cp)​Ru+ and (η5-​Cp*)​Ru+ arenophiles on alkynylnaphthalene: solvent effect on the regioselectivity and the haptotropic rearrangement - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2014

Complexation of the (η5-​Cp)​Ru+ and (η5-​Cp*)​Ru+ arenophiles on alkynylnaphthalene: solvent effect on the regioselectivity and the haptotropic rearrangement

Résumé

The reactions of [Cp*Ru(NCMe)​3]​(PF6) and 1,​4-​R-​C6H4C≡CSiMe3 (R = Me, C≡CSiMe3; Cp* = η5-​C5Me5) in CH2Cl2 provided the complexes [Cp*Ru(η6-​4-​MeC6H4C≡CSiMe3)​]​(PF6) (1) and [Cp*Ru[η6-​1,​4-​C6H4(C≡CSiMe3)​2]​]​(PF6) (2) in 65​% yield. A similar reaction using 1-​(trimethylsilylethynyl)​naphthalene provided the complexes [Cp*Ru(η6-​C10H7C≡CSiMe3)​]​(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 thermodn. ratio is 27​/73. The bis(alkynylnaphthalene) complexes [Cp*Ru(η6-​1,​4-​C10H6(C≡CSiMe3)​2)​]​(PF6) were also obtained in good yields with 4A​/4B kinetic ratios ranging from 80​/20 to 16​/84 depending on the concn. 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 quant. converted to the thermodn. regioisomer 4B. The kinetic products were obtained in less than 4 h at temps. ranging from -​17° to 20°, while the isomerization is much slower. The thermodn. equil. is reached after several days at 20° in a good coordinating solvent such as acetone. The bis(alkynylnaphthalene) was also reacted with [CpRu(NCMe)​3]​(PF6) (Cp = η5-​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 thermodn. ratio was 45​/55. The exptl. data analyzed with the support of theor. calcns. allowed us to propose a mechanism for the reactions of complexation and isomerization.
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Dates et versions

hal-01088623 , version 1 (28-11-2014)

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Rim Makhoul, Jennifer A. Shaw-Taberlet, Hiba Sahnoune, Vincent Dorcet, Samia Kahlal, et al.. Complexation of the (η5-​Cp)​Ru+ and (η5-​Cp*)​Ru+ arenophiles on alkynylnaphthalene: solvent effect on the regioselectivity and the haptotropic rearrangement. Organometallics, 2014, 33 (21), pp.6023-6032. ⟨10.1021/om500654d⟩. ⟨hal-01088623⟩
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