Monocationic μ-diborolyl triple-decker complexes [CpCo(μ-1,3-C3B2Me5)M(ring)]+: synthesis, structures, and electrochemistry

Cationic triple-decker complexes with a bridging diborolyl ligand, [CpCo(μ-1,3-C3B2Me5)M(ring)]+ (M(ring) = CoCp (2a), CoCp* (2b), RhCp (3a), RhCp* (3b), IrCp (4a), IrCp* (4b), Ru(C6H6) (5a), Ru(p-MeC6H4Pri) (5b), Ru(C6Me6) (5c), Ru(η6-cycloheptatriene) (6)), were synthesized by reaction of CpCo(μ-1...

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Hauptverfasser: Muratov, Dmitry V. (VerfasserIn) , Romanov, Alexander S. (VerfasserIn) , Timofeeva, Tatiana V. (VerfasserIn) , Siebert, Walter (VerfasserIn) , Corsini, Maddalena (VerfasserIn) , Fedi, Serena (VerfasserIn) , Zanello, Piero (VerfasserIn) , Kudinov, Alexander R. (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: April 18, 2013
In: Organometallics
Year: 2013, Jahrgang: 32, Heft: 9, Pages: 2713-2724
ISSN:1520-6041
DOI:10.1021/om400178n
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/om400178n
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Verfasserangaben:Dmitry V. Muratov, Alexander S. Romanov, Tatiana V. Timofeeva, Walter Siebert, Maddalena Corsini, Serena Fedi, Piero Zanello, and Alexander R. Kudinov
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Zusammenfassung:Cationic triple-decker complexes with a bridging diborolyl ligand, [CpCo(μ-1,3-C3B2Me5)M(ring)]+ (M(ring) = CoCp (2a), CoCp* (2b), RhCp (3a), RhCp* (3b), IrCp (4a), IrCp* (4b), Ru(C6H6) (5a), Ru(p-MeC6H4Pri) (5b), Ru(C6Me6) (5c), Ru(η6-cycloheptatriene) (6)), were synthesized by reaction of CpCo(μ-1,3-C3B2Me5)Tl with [M(ring)Hal2]2. The structures of 2aBPh4, 2bPF6, 4aPF6, 5aOTf, and 5cPF6 were determined by X-ray diffraction. The electron-transfer ability of the complexes has been ascertained by electrochemical and spectroelectrochemical techniques. In general, they are able to shuttle reversibly in the sequence 2+/+/0/-, plausibly affording completely delocalized mixed-valence derivatives. DFT calculations revealed structural changes accompanying redox processes and satisfactorily predicted the potentials for the first reduction and first oxidation.
Beschreibung:Die Zahlen "3", "2" und "5" sind im Titel tiefgestellt, das Pluszeichen ist hochgestellt
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Beschreibung:Online Resource
ISSN:1520-6041
DOI:10.1021/om400178n