The first triple-decker complex with a carbenium center, (CpCo([mu]-C3B2Me5)RuC5Me4CH2)+: synthesis, reactivity, X-ray structure, and bonding
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...
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
03 July 2017
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| In: |
Chemistry - a European journal
Year: 2017, Volume: 23, Issue: 49, Pages: 11935-11944 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201702571 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1002/chem.201702571 Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201702571 
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| Author Notes: | Dmitry V. Muratov, Alexander S. Romanov, Maddalena Corsini, Alexander R. Kudinov, Fabrizia Fabrizi de Biani, and Walter Siebert |
| Summary: | 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 the crystallographically determined geometry of 2 and allow rationalization of some characteristics of its structure, spectroscopy, and reactivity. |
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| Item Description: | Gesehen am 29.08.2018 Im Titel sind alle Zahlen tiefgestellt, das "+" hochgestellt |
| Physical Description: | Online Resource |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201702571 |