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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Abstract

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
Related URLs:
Depositing User: Pure Connector
Date Deposited: 02 Aug 2017 05:06
Last Modified: 22 Jul 2020 01:42
URI: https://ueaeprints.uea.ac.uk/id/eprint/64325
DOI: 10.1002/chem.201702571

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