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Mononuclear and heterodinuclear phenanthrolinedione complexes of d- and f-block elements

Marco Bortoluzzi, Dario Battistel, Gabriele Albertin, Salvatore Daniele, Francesco Enrichi, and Riccardo Rumonato

Dipartimento di Scienze Molecolari e Nanosistemi, Informatica e Statistica, Università Ca’ Foscari Venezia, Dorsoduro 2137, 30123 Venezia, Italy



Abstract: 1,10-Phenanthroline-5,6-dione (Phd) complexes of group 3 and lanthanide elements having formulae Ln(hfac)3(Phd) (Ln = Y, Eu, Yb; hfac = hexafluoroacetylacetonate) were synthesised and characterised. Complexes of d-block elements of the type [MCl(Phd)(p-cymene)]+ (M = Ru, Os) were also prepared. In all these species, coordination of the polydentate ligand occurs by the N-donor moieties, as indicated by DFT calculations. The novel compounds were tested, together with fac- ReBr(Phd)(CO)3, as precursors for the preparation of heterobimetallic d/f derivatives. The reaction of the rhenium complex with yttrium or lanthanide anhydrous triflate salts led to the formation of the complexes ReBr(CO)3(N,N′-Phd-O,O′)Ln(OTf)3(THF) (Ln = Y, Eu, Yb), where the trivalent ions interacted with the quinonoid moiety. The redox properties of the rhenium centre were strongly affected by the coordination of Ln(OTf)3, as observed by comparing the cyclic voltammetry measurements carried out on fac-ReBr(Phd)(CO)3 and on ReBr(CO)3(N,N′-Phd-O,O′)Y(OTf)3.

Keywords: 1,10-phenanthroline-5,6-dione – d-block elements – lanthanides – heterobimetallic complexes – cyclic voltammetry

Full paper is available at

DOI: 10.1515/chempap-2015-0140


Chemical Papers 70 (1) 43–52 (2016)

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