The first triple-decker complex with a carbenium center, (CpCo([mu]-C3B2Me5)RuC5Me4CH2)+

• Verfasst von: Muratov, Dmitry V. [VerfasserIn]
• Verfasst von: Siebert, Walter [VerfasserIn]
• Titel: The first triple-decker complex with a carbenium center, (CpCo([mu]-C3B2Me5)RuC5Me4CH2)+
• Titelzusatz: synthesis, reactivity, X-ray structure, and bonding
• Verf.angabe: Dmitry V. Muratov, Alexander S. Romanov, Maddalena Corsini, Alexander R. Kudinov, Fabrizia Fabrizi de Biani, and Walter Siebert
• Umfang: 10 S.
• Fussnoten: Gesehen am 29.08.2018 ; Im Titel sind alle Zahlen tiefgestellt, das "+" hochgestellt
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Jahr Quelle: 2017
• Band/Heft Quelle: 23(2017), 49, S. 11935-11944
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201702571
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1580484611

Abstract

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, 7-10 were determined by X-ray diffraction. Density functional calculations support thecrystallographically determined geometry of 2 and allow rationalization of some characteristics of its structure, spectroscopy, and reactivity.