η6-Coordination of a Ruthenium(II) Organometallic Fragment to the Arene Ring of N,C,N-Pincer Metal Complexes

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• 作者：Sylvestre Bonnet ; Martin Lutz ; Anthony L. Spek ; Gerard van Koten ; Robertus J. M. Klein Gebbink
• 刊名：Organometallics
• 出版年：2008
• 出版时间：January 28, 2008
• 年：2008
• 卷：27
• 期：2
• 页码：159 - 162
• 全文大小：106K
• 年卷期：v.27,no.2(January 28, 2008)
• ISSN：1520-6041

文摘

Stable heterobimetallic complexes of the type [MX(NCN)Ru(C₅R₅)]⁺ (R = H or Me), where the phenylene ring of an NCN-pincer ligand coordinates first to a platinum or palladium center via a σ-bond, and second to a ruthenium organometallic fragment via a π-bond, are synthesized in a single step involving electrophilic attack of a cationic Ru species on the aryl metal complex. X-ray crystal structures and solution NMR agree on the simultaneous presence of orthogonal η⁶- and η¹-coordination axes. ¹⁹⁵Pt NMR and electrochemistry show that the η⁶-coordinated ruthenium fragment has a strong electron-withdrawing effect on the pincer metal, which leads to a diminished nucleophilicity of the platinum center toward electrophiles such as SO₂.