Coordination of 12-Electron Organometallic Fragments to the Arene Ring of Nonsymmetric Group 10 POCOP Pincer Complexes

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• 作者：Noel 脕ngel Espinosa-Jalapa ; Sim贸n Hern谩ndez-Ortega ; Xavier-Fred茅ric Le Goff ; David Morales-Morales ; Jean-Pierre Djukic ; Ronan Le Lagadec
• 刊名：Organometallics
• 出版年：2013
• 出版时间：May 13, 2013
• 年：2013
• 卷：32
• 期：9
• 页码：2661-2673
• 全文大小：613K
• 年卷期：v.32,no.9(May 13, 2013)
• ISSN：1520-6041

文摘

A series of heterobimetallic complexes have been prepared in good yields by 畏⁶ coordination of [Cp*Ru]⁺, [CpRu]⁺, [CpFe]⁺, and [Cr(CO)₃] fragments to the aromatic ring of nonsymmetric Ni(II), Pd(II), and Pt(II) naphthoresorcinate POCOP compounds, and the molecular structures of the new compounds have been unequivocally determined by single-crystal X-ray diffraction crystallography. The reaction is regiospecific, and only coordination at the noncyclometalated ring is observed. The coordination occurs in an orthogonal fashion, and as a consequence, the heterobimetallic species exhibit axial desymmetrization of the pincer fragment, generating molecules with planar chirality. In addition, the electronic properties of the metal center can be tuned by the effect of 蟺 coordination of the second metal, as shown by electrochemical studies. The observed specificity of the reaction is discussed and supported with theoretical studies.