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

Muratov, Dmitry V., Romanov, Alexander S., Corsini, Maddalena, Kudinov, Alexander R., Fabrizi de Biani, Fabrizia and Siebert, Walter (2017) The first triple-decker complex with a carbenium center, [CpCo(μ-C3B2Me5)RuC5Me4CH2]+: Synthesis, reactivity, X-ray structure, and bonding. Chemistry - A European Journal, 23 (49). 11935–11944. ISSN 0947-6539

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The first derivative of the methylium cation with the triple-decker substituent, [CpCo(C3B2Me5)RuC5Me4CH2]PF6 ( 2 PF6), 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 2 PF6 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 2 PF6 with nucleophiles OH−, Ph3P, Et3N led to the corresponding derivatives of 1 in high yields. Aromatic amines PhNEt2 and 4-MeC6H4NH2 react with 2 PF6 to give the electrophilic aromatic substitution products quantitatively. Chemical reduction of 2 PF6 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 , 7 – 10 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.

Item Type: Article
Uncontrolled Keywords: boron,cobalt,ruthenium,electrochemistry,triple-decker complex
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
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Depositing User: Pure Connector
Date Deposited: 02 Aug 2017 05:06
Last Modified: 24 Oct 2023 00:56
DOI: 10.1002/chem.201702571


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