Bonding and Substituent Effects in Electron-Rich Mononuclear Ruthenium -Arylacetylides of the Formula [(g src="http://pubs.acs.or

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• 作者：Fré ; dé ; ric Paul ; Benjamin G. Ellis ; Michael I. Bruce ; Loic Toupet ; Thierry Roisnel ; Karine Costuas ; Jean-Franç ; ois Halet ; and Claude Lapinte
• 刊名：Organometallics
• 出版年：2006
• 出版时间：January 30, 2006
• 年：2006
• 卷：25
• 期：3
• 页码：649 - 665
• 全文大小：384K
• 年卷期：v.25,no.3(January 30, 2006)
• ISSN：1520-6041

文摘

This study reports the isolation and the structural (X-ray), UV-vis, and NMR characterization of aseries of electron-rich Ru(II) acetylide complexes of the formula (G SRC="/images/gifchars/eta.gif" BORDER=0 >²-dppe)(ges/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)Ru(Cges/entities/tbd1.gif">C)-1,4-(C₆H₄)X (1a-f; X = NO₂, CN, F, H, OMe, NH₂) and (ges/gifchars/eta.gif" BORDER=0 >²-dppe)(ges/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)Ru(Cges/entities/tbd1.gif">C)-1,3-(C₆H₄)F(1c-m), as well as the spectroscopic (near-IR and ESR) in situ characterization of the correspondingelusive Ru(III) radical cations. The spectroscopic data are discussed in connection with DFT computations,and a consistent picture of the electronic structure of these Ru(II) and Ru(III) acetylide complexes isproposed. Notably, the strong reactivity of the Ru(III) radicals evidenced in this contribution constitutesa major difference with the relative stability of the known iron analogues.