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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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Main Authors: Muratov, Dmitry V. (Author) , Romanov, Alexander S. (Author) , Timofeeva, Tatiana V. (Author) , Siebert, Walter (Author) , Corsini, Maddalena (Author) , Fedi, Serena (Author) , Zanello, Piero (Author) , Kudinov, Alexander R. (Author)
Format: Article (Journal)
Language:English
Published: April 18, 2013
In: Organometallics
Year: 2013, Volume: 32, Issue: 9, Pages: 2713-2724
ISSN:1520-6041
DOI:10.1021/om400178n
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/om400178n
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Author Notes: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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Summary: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.
Item Description:Die Zahlen "3", "2" und "5" sind im Titel tiefgestellt, das Pluszeichen ist hochgestellt
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Physical Description:Online Resource
ISSN:1520-6041
DOI:10.1021/om400178n

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