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Observation of vinylidene emission in mixed phosphine/diimine complexes of Ru(II) at room temperature in solution

The mixed ruthenium(II) complexes trans-[RuCl2(PPh3)2(bipy)] (1), trans-[RuCl2(PPh3)2(Me2bipy)](2), cis-[RuCl2(dcype)(bipy)](3), cis-[RuCl2(dcype)(Me2bipy)](4) (PPh3 = triphenylphosphine, dcype = 1,2-bis(dicyclohexylphosphino)ethane, bipy = 2,2′-bipyridine, Me2bipy = 4,4′-dimethyl-2,2′-bipyridine) w...

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Bibliographic Details
Main Authors: Bogado, André Luiz (Author) , Rominger, Frank (Author)
Format: Article (Journal)
Language:English
Published: 2012
In: Journal of organometallic chemistry
Year: 2011, Volume: 696, Issue: 26, Pages: 4184-4190
ISSN:1872-8561
DOI:10.1016/j.jorganchem.2011.09.017
Online Access:Verlag, Volltext: http://dx.doi.org/10.1016/j.jorganchem.2011.09.017
Verlag, Volltext: http://www.sciencedirect.com/science/article/pii/S0022328X11006061
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Author Notes:André L. Bogado, Rose M. Carlos, Cristina Daólio, Antonio G. Ferreira, Miguel G. Neumann, Frank Rominger, Sergio P. Machado, Juliana P. da Silva, Márcio P. de Araujo, Alzir A. Batista
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Summary:The mixed ruthenium(II) complexes trans-[RuCl2(PPh3)2(bipy)] (1), trans-[RuCl2(PPh3)2(Me2bipy)](2), cis-[RuCl2(dcype)(bipy)](3), cis-[RuCl2(dcype)(Me2bipy)](4) (PPh3 = triphenylphosphine, dcype = 1,2-bis(dicyclohexylphosphino)ethane, bipy = 2,2′-bipyridine, Me2bipy = 4,4′-dimethyl-2,2′-bipyridine) were used as precursors to synthesize the associated vinylidene complexes. The complexes [RuCl(CCHPh)(PPh3)2(bipy)]PF6 (5), [RuCl(CCHPh)(PPh3)2(Me2bipy)]PF6 (6), [RuCl(CCHPh)(dcype)(bipy)]PF6 (7), [RuCl(CCHPh)(dcype)(bipy)]PF6 (8) were characterized and their spectral, electrochemical, photochemical and photophysical properties were examined. The emission assigned to the π-π∗ excited state from the vinylidene ligand is irradiation wavelength (340, 400, 430 nm) and solvent (CH2Cl2, CH3CN, EtOH/MeOH) dependent. The cyclic voltammograms of (6) and (7) show a reversible metal oxidation peak and two successive ligand reductions in the +1.5-(−0.64) V range. The reduction of the vinylidene leads to the formation of the acetylide complex, but due the hydrogen abstraction the process is irreversible. The studies described here suggest that for practical applications such as functional materials, nonlinear optics, building blocks and supramolecular photochemistry.
Item Description:Available online 29 September 2011
Gesehen am 09.10.2018
Physical Description:Online Resource
ISSN:1872-8561
DOI:10.1016/j.jorganchem.2011.09.017

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