Self-Assembled Chloro-Bridged (Arene)ruthenium Metallo-Prisms: Synthesis and Molecular Structure of Cationic Complexes of the Type [Ru6(ages/gifchars/eta.gif

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• 作者：Padavattan Govindaswamy ; Georg S&uuml ; ss-Fink ; Bruno Therrien
• 刊名：Organometallics
• 出版年：2007
• 出版时间：February 12, 2007
• 年：2007
• 卷：26
• 期：4
• 页码：915 - 924
• 全文大小：749K
• 年卷期：v.26,no.4(February 12, 2007)
• ISSN：1520-6041

文摘

Cationic (arene)ruthenium-based hexanuclear complexes with trigonal-prismatic structures have beensynthesized in good yield by self-assembly of only two components: the dinuclear (arene)rutheniumcomplexes [Ru(ages/gifchars/eta.gif" BORDER=0 >⁶-arene)(ages/entities/mgr.gif">-Cl)Cl]₂ (arene = p-PrⁱC₆H₄Me, C₆Me₆) react in water with 2,4,6-tris(pyridinyl)-1,3,5-triazine (tpt) derivatives in the presence of AgO₃SCF₃ to form hexanuclear cations of the generalformula [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-arene)₆(ages/entities/mgr.gif">₃-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆]⁶⁺. In the presence of 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine(4-tpt) the prismatic cations [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-p-PrⁱC₆H₄Me)₆(ages/entities/mgr.gif">₃-4-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆]⁶⁺ (3) and [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-C₆Me₆)₆(ages/entities/mgr.gif">₃-4-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆]⁶⁺ (4) have been isolated as the triflate salts, whereas with 2,4,6-tris(pyridin-3-yl)-1,3,5-triazine (3-tpt) [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-p-PrⁱC₆H₄Me)₆(ages/entities/mgr.gif">₃-3-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆]⁶⁺ (7) and [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-C₆Me₆)₆(ages/entities/mgr.gif">₃-3-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆]⁶⁺ (8) have been obtained and isolated as the triflate salts. In all cases, the neutral intermediatesinitially formed prior to the addition of silver triflate have been isolated and characterized as well: [Ru₃(ages/gifchars/eta.gif" BORDER=0 >⁶-p-PrⁱC₆H₄Me)₃(ages/entities/mgr.gif">₃-4-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)Cl₆] (1), [Ru₃(ages/gifchars/eta.gif" BORDER=0 >⁶-C₆Me₆)₃(ages/entities/mgr.gif">₃-4-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)Cl₆] (2), [Ru₃(ages/gifchars/eta.gif" BORDER=0 >⁶-p-PrⁱC₆H₄Me)₃(ages/entities/mgr.gif">₃-3-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)Cl₆] (5), and [Ru₃(ages/gifchars/eta.gif" BORDER=0 >⁶-C₆Me₆)₃(ages/entities/mgr.gif">₃-3-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)Cl₆] (6), respectively. In the case of a trigonal-prismatic hexacation containing p-cymene and 3-tpt ligands, the NMR spectra reveal a mixture of thetwo isomers 7a and 7b, the formation of which can be rationalized by molecular modeling. The single-crystal structure analyses of [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-p-PrⁱC₆H₄Me)₆(ages/entities/mgr.gif">₃-4-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆][O₃SCF₃]₆ ([3][O₃SCF₃]₆), [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-C₆Me₆)₆(ages/entities/mgr.gif">₃-4-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆][O₃SCF₃]₆ ([4][O₃SCF₃]₆), and [Ru₆(ages/gifchars/eta.gif" BORDER=0 >⁶-C₆Me₆)₆(ages/entities/mgr.gif">₃-3-tpt-ages/gifchars/kappa.gif" BORDER=0 >N)₂(ages/entities/mgr.gif">-Cl)₆][O₃SCF₃]₆ ([8][O₃SCF₃]₆) reveal strong ages/gifchars/pi.gif" BORDER=0 > stacking interactions between the two tpt subunits of the trigonalprisms.