The first triple-decker complex with a carbenium center, [CpCo(μ-C3B2Me5)RuC5Me4CH2]+: Synthesis, reactivity, X-ray structure, and bonding

Dmitry V. Muratov, Alexander S. Romanov, Maddalena Corsini, Alexander R. Kudinov, Fabrizia Fabrizi de Biani, Walter Siebert

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The first derivative of the methylium cation with the triple-decker substituent, [CpCo(C3B2Me5)RuC5Me4CH2]PF6 (2PF6), was synthesized from the reaction of the triple-decker complex CpCo(C3B2Me5)RuCp* (1) with the salt of the trityl cation [CPh3]+. The X-ray crystal structure of 2PF6 reveals that the methylium carbon is bound to the ruthenium with Ru−C bond length of 2.259 Å and corresponds to the description of its structure as η6-fulvene-ruthenium. Reactions of 2PF6 with nucleophiles OH, Ph3P, Et3N led to the corresponding derivatives of 1 in high yields. Aromatic amines PhNEt2 and 4-MeC6H4NH2 react with 2PF6 to give the electrophilic aromatic substitution products quantitatively. Chemical reduction of 2PF6 with Zn powder in tetrahydrofuran leads to the formation of the bis(triple-decker) derivative (CpCo(C3B2Me5)RuC5Me4CH2)2 (10) with a CH2CH2-bridge. The structures of complexes 4, 710 were determined by X-ray diffraction. Density functional calculations support the crystallographically determined geometry of 2 and allow rationalization of some characteristics of its structure, spectroscopy, and reactivity.
Original languageEnglish
Pages (from-to)11935–11944
Number of pages10
JournalChemistry - A European Journal
Issue number49
Early online date9 Aug 2017
Publication statusPublished - 4 Sep 2017


  • Boron
  • Cobalt
  • ruthenium
  • electrochemistry
  • triple-decker complex

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