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Phosphinofulvene Enolate Ligands in Ruthenium Complexes by Ferrocene Photolysis under Solar Radiation
Author(s) -
Carrión M. Carmen,
Torres Javier,
Jalón Félix A.,
Rodríguez Ana M.,
Zirakzadeh Afrooz,
Manzano Blanca R.
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201601440
Subject(s) - chemistry , ruthenium , photochemistry , ligand (biochemistry) , photodissociation , fulvene , moiety , phosphine , stereochemistry , organic chemistry , biochemistry , receptor , catalysis
Ruthenium complexes containing a new type of phosphine ligand were obtained through photochemical transformations. The process involves the irradiation of (phosphinoferrocenylcarbonyl)ruthenium derivatives with visible light (tungsten halogen lamp) to yield complexes with κ 2 ‐ P , O phosphinofulvene enolate ligands after the formal loss of the “CpFe + ” (Cp = cyclopentadienyl) entity. A tandem reaction that involves the irradiation of a mixture of a (hydroxymethyl)ferrocenylphosphine ligand and (arene)ruthenium precursors is also possible. The reaction proceeds through the coordination of the hydroxy phosphine ligands, evolution to hydrido ketone (or hydrido aldehyde) complexes and subsequent evolution to the fulvene derivatives. The process also occurs under solar radiation. The photolysis reaction was studied at different wavelengths of the visible spectrum by irradiation with light‐emitting diodes (LEDs). Positive results were obtained when irradiation was performed in the wavelength region corresponding to the metal‐to‐ligand charge‐transfer (MLCT) band that is characteristic of the acylferrocenyl moiety. The use of green light ( λ = 530 nm) gave the best results, and the reaction did not proceed under higher‐wavelength light or in the dark. A non‐coordinated phosphinoferrocenylcarbaldehyde ligand also evolved under solar radiation, but a complex mixture was obtained; thus, the selectivity increases significantly if the ruthenium centre is present.