Hydrosilylation of Ferrocenylalkyne鈭扗icobalthexacarbonyl Complexes. Model Reactions for the Synthesis of Organometallic Dendrimers

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• 作者：Á ; ngel Nievas ; Jorge J. Gonza虂lez ; Elisa Herna虂ndez ; Esther Delgado ; Avelino Marti虂n ; Carmen M. Casado ; Beatriz Alonso
• 刊名：Organometallics
• 出版年：2011
• 出版时间：April 11, 2011
• 年：2011
• 卷：30
• 期：7
• 页码：1920-1929
• 全文大小：1061K
• 年卷期：v.30,no.7(April 11, 2011)
• ISSN：1520-6041

文摘

Regio- and stereoselective hydrosilylation reactions of ferrocenylalkyne鈭抎icobalthexacarbonyl complexes with HSiEt₃ or dendrimer Si[CH₂CH₂CH₂Si(CH₃)₂H]₄ have afforded the ferrocenylvinylsilanes [FcC(SiEt₃)鈺怌H₂] (1), [FcC鈮C(SiEt₃)鈺怌(H)R] [R = Fc (E-4), H (13), SiMe₃ (Z-15)], and [(E)-FcC(H)鈺怌(SiEt₃)C鈮SiMe₃] (14) and the ferrocenylvinyl-functionalized carbosilane dendrimers Si[CH₂CH₂CH₂Si(CH₃)₂C(Fc)鈺怌H₂]₄ (3) and (Z)-Si[CH₂CH₂CH₂Si(CH₃)₂C{C鈮Fc}鈺怌(H)Fc]₄ (6). Characterization of all compounds by ¹H, ¹³C{¹H}, and ²⁹Si{¹H} NMR and IR spectroscopy, as well as mass spectrometry, supports their assigned structures. The molecular structures of compounds [{Co₃(CO)₉}(渭₃-CCH₂Fc)] (2), [C(O)C(Fc)鈺怌(SiEt₃)C鈺怌(H)Fc] (5), [{Co₂(CO)₆}(渭,畏²-FcC鈮CCH)] (8), and [{Co₂(CO)₆}₂(渭,畏²,畏²-FcCCCCSiMe₃)] (9) have been determined by single-crystal X-ray diffraction. The redox activity of the model diferrocenylalkynyl complex 4 and the corresponding octaferrocenyl dendrimer 6 has been examined by cyclic voltammetry.